[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

WO2022194843A1 - 1,2,4-thiadiazoles substitués, leurs sels et leur utilisation comme substances actives herbicides - Google Patents

1,2,4-thiadiazoles substitués, leurs sels et leur utilisation comme substances actives herbicides Download PDF

Info

Publication number
WO2022194843A1
WO2022194843A1 PCT/EP2022/056653 EP2022056653W WO2022194843A1 WO 2022194843 A1 WO2022194843 A1 WO 2022194843A1 EP 2022056653 W EP2022056653 W EP 2022056653W WO 2022194843 A1 WO2022194843 A1 WO 2022194843A1
Authority
WO
WIPO (PCT)
Prior art keywords
represents hydrogen
methyl
cycloalkyl
alkyl
haloalkyl
Prior art date
Application number
PCT/EP2022/056653
Other languages
English (en)
Inventor
David Michael BARBER
Jhi AMETOVSKI
Stefan Schnatterer
Anu Bheemaiah MACHETTIRA
Elisabeth ASMUS
Christopher Hugh Rosinger
Elmar Gatzweiler
Dirk Schmutzler
Anna Maria REINGRUBER
Birgit BOLLENBACH-WAHL
Jan Dittgen
Original Assignee
Bayer Aktiengesellschaft
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 Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Publication of WO2022194843A1 publication Critical patent/WO2022194843A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/08—1,2,4-Thiadiazoles; Hydrogenated 1,2,4-thiadiazoles
    • 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

Definitions

  • the invention relates to the technical field of herbicides and/or plant growth regulators. Specifically, the invention primarily relates to substituted 1,2,4-thiadiazoles, and compositions comprising said substituted 1,2,4-thiadiazoles. In addition, the present invention relates to processes for the preparation of said substituted 1,2,4-thiadiazoles and their use as herbicides and/or plant growth regulators.
  • crop protection agents that are known to date for the selective control of harmful plants in crops of useful plants or active compounds for controlling unwanted vegetation sometimes have disadvantages, be it (a) that they have no or insufficient herbicidal activity against particularly harmful plants, (b) that the spectrum of harmful plants which can be controlled with an active compound is not broad enough, (c) that their selectivity in crops of useful plants is too low and/or (d) that they have a toxicologically unfavourable profile.
  • active compounds which can be used as plant growth regulators for a number of useful plants cause an unwanted reduction of harvest yields in other useful plants or are not compatible with the crop plant, or only within a narrow application rate range.
  • active compounds cannot be produced economically on an industrial scale owing to precursors and reagents which are difficult to obtain, or that they have only insufficient chemical stabilities.
  • EP 0049071 US 4416683, US 4515625, US 4636243 and US 4801718 relate to heterocyclic substituted N-benzamides and their use as herbicides.
  • DE 2154852 discloses certain 5-substituted amino-3-isopropyl- 1,2,4-thiadiazoles and their uses as pesticides and herbicides.
  • DE 19601139 concerns the preparation of acylated 5-amino- 1,2,4-thiadiazoles and their use as pesticides.
  • WO 01/36415, WO 01/40206, WO 01/40223, and WO 01/46165 describe several substituted 1,2,4- thiadiazoles that are suitable for controlling pests.
  • WO 2017/005717 and WO 2018/108791 relate to aromatic and heteroaromaticsubstituted 1,2,4- thiadiazoles and their use as pesticidally active compounds.
  • the present invention accordingly provides substituted 1,2,4-thiadiazoles of the general formula (I), or salts thereof, in which W represents oxygen or sulfur, R 1 represents hydrogen, halogen, cyano, methyl, ethyl, (C 3 -C 6 )-cycloalkyl, (C 3 -C 6 )-halocycloalkyl, (C 1 -C 4 )-alkoxy or (C 1 -C 4 )-haloalkoxy, R 2 represents (C2-C4)-alkenyl, (C2-C4)-haloalkenyl, (C1-C4)-haloalkyl-(C2-C4)-alkenyl, (C3-C6)- cycloalkyl, (C3-C6)-halocycloalkyl, (C1-C4)-alkyl-(C3-C6)-cycloalkyl, (C1-C4)-alkyl-(C3-C6)-halocycloalkyl, (C
  • the compounds of the general formula (I) can form salts by addition of a suitable inorganic or organic acid, for example mineral acids, for example HCl, HBr, H 2 SO 4 , H 3 PO 4 or HNO 3 , or organic acids, for example carboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid, lactic acid or salicylic acid or sulfonic acids, for example p-toluenesulfonic acid, onto a basic group, for example amino, alkylamino, dialkylamino, piperidino, morpholino or pyridino.
  • these salts will comprise the conjugated base of the acid as the anion.
  • Suitable substituents in deprotonated form are capable of forming internal salts with groups, such as amino groups, which are themselves protonatable. Salts may also be formed by action of a base on compounds of the general formula (I).
  • Suitable bases are, for example, organic amines such as trialkylamines, morpholine, piperidine and pyridine, and the hydroxides, carbonates and bicarbonates of ammonium, alkali metals or alkaline earth metals, especially sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
  • salts are compounds in which the acidic hydrogen is replaced by an agriculturally suitable cation, for example metal salts, especially alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or else ammonium salts, salts with organic amines or quaternary ammonium salts, for example with cations of the formula [NR a R b R c R d ] + in which R a to R d are each independently an organic radical, especially alkyl, aryl, arylalkyl or alkylaryl.
  • an agriculturally suitable cation for example metal salts, especially alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or else ammonium salts, salts with organic amines or quaternary ammonium salts, for example with cations of the formula [NR a R b R c R d ] + in which R a to R d are each independently an organic radical, especially alkyl, aryl,
  • alkylsulfonium and alkylsulfoxonium salts such as (C1-C4)-trialkylsulfonium and (C1-C4)- trialkylsulfoxonium salts.
  • the substituted 1,2,4-thiadiazoles of the general formula (I) according to the invention can, depending on external conditions such as pH, solvent and temperature, be present in various tautomeric structures, all of which are embraced by the general formula (I).
  • the compounds of the formula (I) used in accordance with the invention and salts thereof are also referred to hereinafter as "compounds of the general formula (I)".
  • the invention preferably provides compounds of the general formula (I), or salts thereof in which W represents oxygen or sulfur, R 1 represents hydrogen, halogen, methyl, ethyl, (C 3 -C 6 )-cycloalkyl or (C 1 -C 4 )-alkoxy, R 2 represents (C2-C4)-alkenyl, (C2-C4)-haloalkenyl, (C1-C4)-haloalkyl-(C2-C4)-alkenyl, (C3-C6)- cycloalkyl, (C3-C6)-halocycloalkyl, (C1-C4)-alkyl-(C3-C6)-cycloalkyl, (C1-C4)-alkyl-(C3-C6)- halocycloalkyl, (C1-C4)-haloalkyl-(C3-C6)-cycloalkyl, (C1-C4)-haloalkyl-(C3-C6)-cycloalky
  • the invention particularly provides compounds of the general formula (I), or salts thereof in which W represents oxygen or sulfur, preferably oxygen, R 1 represents hydrogen, halogen, methyl or (C3-C6)-cycloalkyl, R 2 represents (C 2 -C 4 )-alkenyl, (C 2 -C 4 )-haloalkenyl, (C 1 -C 4 )-haloalkyl-(C 2 -C 4 )-alkenyl, (C 3 -C 6 )- cycloalkyl, (C 3 -C 6 )-halocycloalkyl, (C 1 -C 4 )-alkyl-(C 3 -C 6 )-cycloalkyl, (C 1 -C 4 )-alkyl-(C 3 -C 6 )- halocycloalkyl or (C 3 -C 6 )-cycloalkyl-(C 3 -C 6 )-cycloalkyl, R 3 represents hydrogen or
  • the invention more particularly provides compounds of the general formula (I), or salts thereof in which W represents oxygen, R 1 represents hydrogen, chlorine, bromine, methyl or cyclopropyl, R 2 represents vinyl, 1-fluorovinyl, 2,2-difluorovinyl, trifluoromethylvinyl, prop-1-en-2-yl, cyclopropyl, 2-methylcyclopropyl, 2,2-dimethylcyclopropyl, 2,2-difluorocyclopropyl, 2,2- dichlorocyclopropyl, 2,2-difluoro-1-methyl-cyclopropyl, 2-cyclopropylcyclopropyl, cyclobutyl or cyclopentyl, R 3 represents hydrogen or fluorine, R 4 represents hydrogen, fluorine, chlorine or trifluoromethyl, R 5 represents hydrogen, fluorine or chlorine, and R 6 represents hydrogen or fluorine.
  • W represents oxygen
  • R 1 represents hydrogen, chlorine, bromine, methyl or cyclopropyl
  • the invention especially provides compounds of the general formula (I), or salts thereof in which W represents oxygen, R 1 represents hydrogen, chlorine, bromine or methyl, R 2 represents vinyl, 1-fluorovinyl, 2,2-difluorovinyl, trifluoromethylvinyl, prop-1-en-2-yl, cyclopropyl, 2-methylcyclopropyl, 2,2-dimethylcyclopropyl, 2,2-difluorocyclopropyl, 2,2- dichlorocyclopropyl, 2,2-difluoro-1-methyl-cyclopropyl or cyclopentyl, R 3 represents hydrogen or fluorine, R 4 represents hydrogen, fluorine, chlorine or trifluoromethyl,
  • R 5 represents hydrogen, fluorine or chlorine
  • R 6 represents hydrogen or fluorine
  • radicals listed above in general terms or within areas of preference apply both to the end products of the general formula (I) and correspondingly to the starting materials or intermediates required for preparation in each case. These radical definitions can be combined with one another as desired, i.e. including combinations between the given preferred ranges.
  • names of chemical groups are generally to be understood such that attachment to the skeleton or the remainder of the molecule is via the structural element mentioned last, i.e. for example in the case of (C2-Cs)-alkoxy via the oxygen atom and in the case of aryl-(Ci-Cs)-alkyl or (C3-C6)cycloalkyl-(Ci-Cs)-alkyl in each case via the carbon atom of the alkyl group.
  • Alkoxy denotes an alkyl radical bonded via an oxygen atom, for example (but not limited to) (CVG,)- alkoxy such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy,
  • Alkenoxy denotes an alkenyl radical attached via an oxygen atom
  • alkynoxy denotes an alkynyl radical attached via an oxygen atom, such as (C2-Cs)-, (CVG,)- or (C2-C4)-alkenoxy and (C3-C8)-, (C3-C6)- or (C3-C4)-alkynoxy.
  • halogen denotes, for example, fluorine, chlorine, bromine or iodine. If the term is used for a radical, "halogen” denotes, for example, a fluorine, chlorine, bromine or iodine atom.
  • alkyl denotes a straight-chain or branched open-chain, saturated hydrocarbon radical which is optionally mono- or polysubstituted, and in the latter case is referred to as "substituted alkyl".
  • Preferred substituents are halogen atoms, alkoxy, haloalkoxy, cyano, alkylthio, haloalkylthio, amino or nitro groups, particular preference being given to methoxy, methyl, fluoroalkyl, cyano, nitro, fluorine, chlorine, bromine or iodine.
  • the prefix “bis” also includes the combination of different alkyl radicals, e.g. methyl(ethyl) or ethyl(methyl).
  • Haloalkyl "-alkenyl” and “-alkynyl” respectively denote alkyl, alkenyl and alkynyl partially or fully substituted by identical or different halogen atoms, for example monohaloalkyl such as CH2CH2CI, CH 2 CH 2 Br, CHCICH3, CH2CI, CH 2 F; perhaloalkyl such as CC1 3, CC1F 2, CFC1 2 ,CF 2 CC1F 2, CF 2 CC1FCF 3 ; polyhaloalkyl such as CH2CHFCI, CF2CCIFH, CF2CBrFH, CH2CF3; the term perhaloalkyl also encompasses the term perfluoroalkyl.
  • monohaloalkyl such as CH2CH2CI, CH 2 CH 2 Br, CHCICH3, CH2CI, CH 2 F
  • perhaloalkyl such as CC1 3, CC1F 2, CFC1 2 ,CF 2 CC1F 2, CF 2
  • Haloalkoxy is, for example, OCF3, OCHF2, OCH2F, OCF2CF3, OCH2CF3 and OCH2CH2CI; this applies correspondingly to haloalkenyl and other halogen-substituted radicals.
  • (Ci-C4)-alkyl is a brief notation for straight-chain or branched alkyl having one to 4 carbon atoms according to the range stated for carbon atoms, i.e. encompasses the methyl, ethyl, 1 -propyl, 2-propyl, 1 -butyl, 2-butyl, 2-methylpropyl or tert-butyl radicals.
  • General alkyl radicals with a larger specified range of carbon atoms e.g. "(Ci-C 6 )-alkyl”
  • correspondingly also encompass straight-chain or branched alkyl radicals with a greater number of carbon atoms i.e. according to the example also the alkyl radicals having 5 and 6 carbon atoms.
  • the lower carbon skeletons for example having from 1 to 6 carbon atoms, or having from 2 to 6 carbon atoms in the case of unsaturated groups, in the case of the hydrocarbyl radicals such as alkyl, alkenyl and alkynyl radicals, including in composite radicals.
  • Alkyl radicals including in composite radicals such as alkoxy, haloalkyl, etc., are, for example, methyl, ethyl, n-propyl or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls such as n-hexyl, i-hexyl and 1,3- dimethylbutyl, heptyls such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl; alkenyl and alkynyl radicals are defined as the possible unsaturated radicals corresponding to the alkyl radicals, where at least one double bond or triple bond is present.
  • radicals having one double bond or triple bond Preference is given to radicals having one double bond or triple bond.
  • alkenyl also includes, in particular, straight-chain or branched open-chain hydrocarbon radicals having more than one double bond, such as 1,3-butadienyl and 1,4-pentadienyl, but also allenyl or cumulenyl radicals having one or more cumulated double bonds, for example allenyl (1,2- propadienyl), 1,2-butadienyl and 1,2,3-pentatrienyl.
  • Alkenyl denotes, for example, vinyl which may optionally be substituted by further alkyl radicals, for example (but not limited thereto) (C 2 -C 6 )-alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1- propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3- pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-d
  • cycloalkyl denotes a carbocyclic saturated ring system having preferably 3-8 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, which optionally has further substitution, preferably by hydrogen, alkyl, alkoxy, cyano, nitro, alkylthio, haloalkylthio, halogen, alkenyl, alkynyl, haloalkyl, amino, alkylamino, bisalkylamino, alkoxycarbonyl, hydroxycarbonyl, arylalkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, cycloalkylaminocarbonyl.
  • cyclic systems with substituents are included, also including substituents with a double bond on the cycloalkyl radical, for example an alkylidene group such as methylidene.
  • polycyclic aliphatic systems are also included, for example bicyclo[1.1.0]butan-1-yl, bicyclo[1.1.0]butan-2-yl, bicyclo[2.1.0]pentan-1-yl, bicyclo[1.1.1]pentan-1-yl, bicyclo[2.1.0]pentan-2-yl, bicyclo[2.1.0]pentan-5-yl, bicyclo[2.1.1]hexyl, bicyclo[2.2.1]hept-2-yl, bicyclo[2.2.2]octan-2-yl, bicyclo[3.2.1]octan-2-yl, bicyclo[3.2.2]nonan-2-yl, a
  • (C3-C7)-cycloalkyl is a brief notation for cycloalkyl having three to 7 carbon atoms, corresponding to the range specified for carbon atoms.
  • substituted cycloalkyl spirocyclic aliphatic systems are also included, for example spiro[2.2]pent-l-yl, spiro[2.3]hex-l-yl, spiro[2.3]hex-4-yl, 3-spiro[2.3]hex-5-yl, spiro[3.3]hept-l-yl, spiro[3.3]hept-2-yl.
  • Halocycloalkyl and halocycloalkenyl denote cycloalkyl and cycloalkenyl, respectively, which are partially or fully substituted by identical or different halogen atoms, such as F, Cl and Br, or by haloalkyl, such as trifluoromethyl or difluoromethyl, for example 1-fluorocycloprop-l-yl, 2- fluorocycloprop- 1 -yl, 2,2-difluorocycloprop- 1 -yl, 1 -fluorocyclobut- 1 -yl, 1 -trifluoromethylcycloprop- 1 - yl, 2-trifluoromethylcycloprop-l-yl, 1-chlorocycloprop-l-yl, 2-chlorocycloprop-l-yl, 2,2- dichlorocycloprop-l-yl, 3,3-difluorocyclobutyl.
  • the compounds of the general formula (I) may be present as stereoisomers.
  • the general formula (I) embraces all possible stereoisomers defined by the specific three-dimensional form thereof, such as enantiomers, diastereomers, Z and E isomers. If, for example, one or more alkenyl groups are present, diastereomers (Z and E isomers) may occur. If, for example, one or more asymmetric carbon atoms are present, enantiomers and diastereomers may occur.
  • Stereoisomers can be obtained from the mixtures obtained in the preparation by customary separation methods.
  • the chromatographic separation can be affected either on the analytical scale to find the enantiomeric excess or the diastereomeric excess, or else on the preparative scale to produce test specimens for biological testing. It is likewise possible to selectively prepare stereoisomers by using stereoselective reactions with use of optically active starting materials and/or auxiliaries.
  • the invention thus also relates to all stereoisomers which are embraced by the general formula (I) but are not shown in their specific stereomeric form, and to mixtures thereof.
  • the purification can also be carried out by recrystallization or digestion. If individual compounds (I) cannot be obtained in a satisfactory manner by the routes described below, they can be prepared by derivatization of other compounds (I).
  • Suitable isolation methods, purification methods and methods for separating stereoisomers of compounds of the general formula (I) are methods generally known to the person skilled in the art from analogous cases, for example by physical processes such as crystallization, chromatographic methods, in particular column chromatography and HPLC (high pressure liquid chromatography), distillation, optionally under reduced pressure, extraction and other methods, any mixtures that remain can generally be separated by chromatographic separation, for example on chiral solid phases.
  • Suitable for preparative amounts or on an industrial scale are processes such as crystallization, for example of diastereomeric salts which can be obtained from the diastereomer mixtures using optically active acids and, if appropriate, provided that acidic groups are present, using optically active bases.
  • the substituted 1,2,4-thiadiazoles of the general formula (I) according to the invention can be prepared using known processes.
  • the synthesis routes used and examined proceed from commercially available or easily synthesised substituted 1,2,4-thiadiazoles, or salts thereof (e.g. hydrochloride or dihydrochloride) and substituted carboxylic acids.
  • the groups R 1 , R 2 , R 3 , R 4 , R 5 and R 6 of the general formula (I) have the meanings defined above, unless exemplary, but not limiting definitions are given.
  • the first synthesis route for substituted 1,2,4-thiadiazoles of the general formula (I) proceeds via an optionally substituted aminothiadiazole (II), or salt thereof and an optionally substituted carboxylic acid (III) (Scheme 1).
  • a substituted aminothiadiazole is reacted with a substituted carboxylic acid in the presence of a suitable coupling reagent (e.g. thionyl chloride) and a suitable base (e.g. 1 -methyl- lH-imidazole) to afford the target 1,2,4-thiadiazoles (I) (cf. US2019/0233382).
  • a suitable coupling reagent e.g. thionyl chloride
  • a suitable base e.g. 1 -methyl- lH-imidazole
  • a salt of the aminothiadiazole can be used, with the free amine being generated in the reaction mixture.
  • a plethora of amide coupling reagents and bases exist that could be used to achieve this reaction cf. Chem. Soc. Rev., 2009, 38, 606-631).
  • Suitable amide coupling reagents include but are not limited to oxalyl chloride, T3P (propanephosphonic acid anhydride), DIC (1,3-diisopropylcarbodiimide) and HATU (l-[bis(dimethylamino)methylene]-lH-l,2,3-triazolo[4,5- bjpyridinium 3-oxide hexafluorophosphate) and other suitable bases include but are not limited to trie thy lamine, DIPEA (N,N-diisopropylethylamine) and pyridine.
  • substituted 1,2,4-thiadiazoles of the general formula (I) can alternatively be completed via direct amide coupling of an optionally substituted acid chloride (IV) with an optionally substituted 1,2,4-thiadiazole (II) (Scheme 2).
  • a base e.g. triethylamine
  • THF tetrahydrofuran
  • substituted 1,2,4-thiadiazoles of the general formula (I) can, in addition, be achieved by the direct amide coupling of a substituted 1,2,4-thiadiazole (II) with an optionally substituted ester (V) (Scheme 3).
  • an appropriate reagent e.g. trimethylaluminium
  • a suitable solvent e.g. dichloromethane or toluene
  • This transformation can also be accomplished using a variety of other reagents that are known in the literature (cf. Tetrahedron Lett., 2006, 47, 5767-5769).
  • substituted 1,2,4-thiadiazoles of the general formula (I) can also be accomplished by independently preparing the optionally substituted carboxylic acid and then conducting the crucial amide coupling with a substituted 1,2,4-thiadiazole.
  • carboxylic acid (VI) is converted to methyl ester (VII) using a suitable chlorinating reagent (e.g. thionyl chloride) and methanol.
  • a suitable chlorinating reagent e.g. thionyl chloride
  • Ester (VII) is then coupled with cyclopropyl boronic acid (VIII) in a Suzuki-Miyaura cross coupling reaction using a suitable palladium complex (e.g. Pd(dppf)Cl2), an appropriate base (e.g.
  • the synthesis of substituted 1,2,4-thiadiazoles of the general formula (I) can furthermore be completed using other known cross-coupling reactions to prepare the optionally substituted carboxylic acids needed for the final amide coupling reaction.
  • Such examples include, but are not limited to, the Heck reaction (cf. J. Org. Chem., 2011, 76, 8036-8041), Hiyama cross-coupling (cf. J. Am. Chem. Soc., 2003, 125, 5616-5617), Stille cross-coupling (cf. Angew. Chem. Int. Ed., 2004, 43, 1132-1136) and the Negishi cross-coupling (cf. J. Am. Chem. Soc., 2004, 126, 13028-13032).
  • R 3 , R 4 , R 5 and R 6 have the meanings defined above.
  • R 7 by way of example and not by limitation, represent hydrogen or methyl.
  • R 8 and R 9 by way of example and not by limitation, represent hydrogen, fluorine or methyl.
  • the alkenyl substituted phenyl ester (XIII) can also be further derivitised to prepare carboxylic acids bearing substituted cyclopropyl substituents that can be be used to synthesise substituted 1,2,4- thiadiazoles of the general formula (I).
  • a suitable reagent e.g. sodium chlorodifluoroacetate or chloroform
  • R 7 by way of example and not by limitation, represents hydrogen.
  • R 8 and R 9 by way of example and not by limitation, represent hydrogen.
  • the resulting mixture was heated to 95 °C for 16 h.
  • the reaction mixture was diluted with water (20 mL) and CH2CI2 (20 mL) and then filtered through a pad of celite. The phases were separated and the aqueous phase was extracted with CH2CI2 (3 x 10 mL). The combined organic extracts were dried over Na2SC>4, filtered and concentrated under reduced pressure.
  • the resulting residue was purified via flash column chromatography on silica gel eluting with n-heptane/EtOAc (100:0 ® 95:5) to afford compound XHIb (362 mg, 38% yield) as a colourless oil.
  • XVa methyl 2-(2,2-difluorocyclopropyl)benzoate
  • THF 3 mL
  • sodium chlorodifluoroacetate 282 mg, 1.85 mmol, 3 eq.
  • the reaction mixture was cooled to RT and the pressure of the microwave vial was relieved.
  • reaction mixture was diluted with a mixture of water/Et 2 O (1:1, 8 mL) and extracted with Et 2 O (3 ⁇ 10 mL). The combined organic extracts were dried over Na2SO4, filtered and concentrated under reduced pressure. The resulting residue was purified via flash column chromatography on silica gel eluting with n-heptane/EtOAc (100:0 ⁇ 95:5) to afford compound XVa (61 mg, 47% yield) as a colourless oil.
  • reaction mixture was diluted with water (5 mL) and extracted with CH 2 Cl 2 (5 mL). The organic extract was concentrated under reduced pressure and the resulting residue was purified via flash column chromatography on silica gel eluting with n-heptane/EtOAc (100:0 ⁇ 50:50) to afford compound I-019 (50 mg, 74% yield) as a white solid.
  • XVb methyl 2-(2,2-dichlorocyclopropyl)benzoate
  • methyl 2-vinylbenzoate 200 mg, 1.23 mmol, 1 eq.
  • tetra-n-butylammonium bromide 16 mg, 0.04 mmol, 0.04 eq.
  • CHCl 3 10 mL
  • tetra-n-butylammonium bromide 16 mg, 0.04 mmol, 0.04 eq.
  • Table 1 Examples of preferred compounds of the general formula (I) Spectroscopic data of selected table examples: The spectroscopic data listed hereinafter for selected table examples were evaluated via conventional 1 H-NMR interpretation or via NMR peak list methods.
  • I-011 1 H-NMR (400 MHz, CDCl3): ⁇ H 13.09 (br. s, 1H), 7.68-7.65 (m, 2H), 7.05-7.01 (m, 1H), 6.81-6.77 (m, 1H), 2.41-2.37 (m, 1H), 1.11-1.06 (m, 2H), 0.79-0.75 (m, 2H).
  • I-036 1 H-NMR (400 MHz, DMSO-d6): ⁇ H 8.59 (s, 1H), 7.71-7.64 (m, 1H), 7.31-7.28 (m, 1H), 3.07- 2.99 (m, 1H), 2.05-1.93 (m, 2H). No.
  • I-042 1 H-NMR (400 MHz, CDCl 3 ): ⁇ H 12.98 (br. s, 1H), 7.94-7.24 (m, 5H), 4.24-3.96 (m, 1H), 2.39-2.29 (m, 2H), 2.17-1.91 (m, 3H).1.83-1.76 (m, 1H).
  • ⁇ -value in ppm and the signal intensity in round brackets. Between the ⁇ -value – signal intensity pairs are semicolons as delimiters.
  • the peak list of an example has therefore the form: ⁇ 1 (intensity1); ⁇ 2 (intensity2);........; ⁇ i (intensityi); hence; ⁇ n (intensityn)
  • Intensity of sharp signals correlates with the height of the signals in a printed example of a NMR spectrum in cm and shows the real relations of signal intensities. From broad signals several peaks or the middle of the signal and their relative intensity in comparison to the most intensive signal in the spectrum can be shown.
  • tetramethylsilane peak can occur but not necessarily.
  • the 1 H-NMR peak lists are similar to classical 1 H-NMR prints and contains therefore usually all peaks, which are listed at classical NMR-interpretation. Additionally, they can show like classical 1 H-NMR prints signals of solvents, stereoisomers of the target compounds, which are also object of the invention, and/or peaks of impurities.
  • peaks of solvents for example peaks of DMSO in DMSO-d 6 and the peak of water are shown in our 1 H-NMR peak lists and have usually on average a high intensity.
  • the peaks of stereoisomers of the target compounds and/or peaks of impurities have usually on average a lower intensity than the peaks of target compounds (for example with a purity >90%).
  • Such stereoisomers and/or impurities can be typical for the specific preparation process. Therefore, their peaks can help to recognize the reproduction of our preparation process via “side-products-fingerprints”.
  • the present invention provides the use of one or more compounds of the general formula (I) and/or salts thereof, as defined above, preferably in one of the embodiments identified as preferred or particularly preferred, in particular one or more compounds of the formulae (1-001) to (1-051) and/or salts thereof, in each case as defined above, as herbicide and/or plant growth regulator, preferably in crops of useful plants and/or ornamental plants.
  • the present invention furthermore provides a method for controlling harmful plants and/or for regulating the growth of plants, characterized in that an effective amount of one or more compounds of the general formula (I) and/or salts thereof, as defined above, preferably in one of the embodiments identified as preferred or particularly preferred, in particular one or more compounds of the formulae (1-001) to (1-051) and/or salts thereof, in each case as defined above, or of a composition according to the invention, as defined below, is applied to the (harmful) plants, seeds of (harmful) plants, the soil in which or on which the (harmful) plants grow or the area under cultivation.
  • an effective amount of one or more compounds of the general formula (I) and/or salts thereof, as defined above preferably in one of the embodiments identified as preferred or particularly preferred, in particular one or more compounds of the formulae (1-001) to (1-051) and/or salts thereof, in each case as defined above, or of a composition according to the invention, as defined below, is applied to the (harmful) plants, seeds
  • the present invention also provides a method for controlling unwanted plants, preferably in crops of useful plants, characterized in that an effective amount of one or more compounds of the general formula (I) and/or salts thereof, as defined above, preferably in one of the embodiments identified as preferred or particularly preferred, in particular one or more compounds of the formulae (1-001) to (1-051) and/or salts thereof, in each case as defined above, or of a composition according to the invention, as defined below, is applied to unwanted plants (for example harmful plants such as mono- or dicotyledonous weeds or unwanted crop plants), the seed of the unwanted plants (i.e.
  • plant seeds for example grains, seeds or vegetative propagation organs such as tubers or shoot parts with buds
  • the soil in which or on which the unwanted plants grow for example the soil of crop land or non-crop land
  • the area under cultivation i.e. the area on which the unwanted plants will grow.
  • the present invention furthermore also provides methods for regulating the growth of plants, preferably of useful plants, characterized in that an effective amount of one or more compounds of the general formula (I) and/or salts thereof, as defined above, preferably in one of the embodiments identified as preferred or particularly preferred, in particular one or more compounds of the formulae (1-001) to (1-051) and/or salts thereof, in each case as defined above, or of a composition according to the invention, as defined below, is applied to the plant, the seed of the plant (i.e. plant seed, for example grains, seeds or vegetative propagation organs such as tubers or shoot parts with buds), the soil in which or on which the plants grow (for example the soil of crop land or non-crop land) or the area under cultivation (i.e. the area on which the plants will grow).
  • the seed of the plant i.e. plant seed, for example grains, seeds or vegetative propagation organs such as tubers or shoot parts with buds
  • the soil in which or on which the plants grow for example the soil of crop land
  • the compounds according to the invention or the compositions according to the invention can be applied for example by pre-sowing (if appropriate also by incorporation into the soil), pre emergence and/or post-emergence processes.
  • pre-sowing if appropriate also by incorporation into the soil
  • pre emergence and/or post-emergence processes Specific examples of some representatives of the monocotyledonous and dicotyledonous weed flora which can be controlled by the compounds according to the invention are as follows, though there is no intention to restrict the enumeration to particular species.
  • one or more compounds of the general formula (I) and/or salts thereof are preferably employed for controlling harmful plants or for regulating growth in crops of useful plants or ornamental plants, where in a preferred embodiment the useful plants or ornamental plants are transgenic plants.
  • the compounds of the general formula (I) according to the invention and/or their salts are suitable for controlling the following genera of monocotyledonous and dicotyledonous harmful plants:
  • Monocotyledonous harmful plants of the genera Aegilops, Agropyron, Agrostis, Alopecurus, Apera,
  • the compounds according to the invention are applied to the soil surface before germination of the harmful plants (weed grasses and/or broad-leaved weeds) (pre-emergence method), either the seedlings of the weed grasses or broad-leaved weeds are prevented completely from emerging or they grow until they have reached the cotyledon stage, but then stop growing and eventually, after three to four weeks have elapsed, die completely.
  • the harmful plants weed grasses and/or broad-leaved weeds
  • the active compounds are applied post-emergence to the green parts of the plants, growth stops after the treatment, and the harmful plants remain at the growth stage at the time of application, or they die completely after a certain time, so that in this manner competition by the weeds, which is harmful to the crop plants, is eliminated very early and in a sustained manner.
  • the compounds according to the invention display an outstanding herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of economically important crops, for example dicotyledonous crops of the genera Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Miscanthus, Nicotiana, Phaseolus,
  • the present compounds are very suitable for selective control of unwanted plant growth in plant crops such as agriculturally useful plants or ornamental plants.
  • the compounds of the invention (depending on their particular structure and the application rate deployed) have outstanding growth-regulating properties in crop plants. They intervene in the plants’ own metabolism with regulatory effect and can thus be used for the controlled influencing of plant constituents and to facilitate harvesting, for example by triggering desiccation and stunted growth. Furthermore, they are also suitable for the general control and inhibition of unwanted vegetative growth without killing the plants in the process. Inhibition of vegetative growth plays a major role for many mono- and dicotyledonous crops since, for example, this can reduce or completely prevent lodging.
  • the active compounds can also be used to control harmful plants in crops of genetically modified plants or plants modified by conventional mutagenesis.
  • the transgenic plants are characterized by particular advantageous properties, for example by resistances to certain pesticides, in particular certain herbicides, resistances to plant diseases or pathogens of plant diseases, such as certain insects or microorganisms such as fungi, bacteria or viruses.
  • Other specific characteristics relate, for example, to the harvested material with regard to quantity, quality, storability, composition and specific constituents. For instance, there are known transgenic plants with an elevated starch content or altered starch quality, or those with a different fatty acid composition in the harvested material.
  • transgenic crops it is preferred with a view to transgenic crops to use the compounds according to the invention and/or their salts in economically important transgenic crops of useful plants and ornamentals, for example of cereals such as wheat, barley, rye, oats, millet, rice and corn or else crops of sugar beet, cotton, soybean, oilseed rape, potato, tomato, peas and other vegetables.
  • cereals such as wheat, barley, rye, oats, millet, rice and corn or else crops of sugar beet, cotton, soybean, oilseed rape, potato, tomato, peas and other vegetables.
  • the active compounds can also be used to control harmful plants in crops of genetically modified plants which are known or are yet to be developed.
  • the transgenic plants are characterized by particular advantageous properties, for example by resistances to certain pesticides, in particular certain herbicides, resistances to plant diseases or pathogens of plant diseases, such as certain insects or microorganisms such as fungi, bacteria or viruses.
  • Other specific characteristics relate, for example, to the harvested material with regard to quantity, quality, storability, composition and specific constituents. For instance, there are known transgenic plants with an elevated starch content or altered starch quality, or those with a different fatty acid composition in the harvested material.
  • Further special properties may be tolerance or resistance to abiotic stressors, for example heat, cold, drought, salinity and ultraviolet radiation.
  • cereals such as wheat, barley, rye, oats, triticale, millet, rice, cassava and corn, or else crops of sugar beet, cotton, soybean, oilseed rape, potatoes, tomatoes, peas and other vegetables.
  • the compounds of the general formula (I) can preferably be used as herbicides in crops of useful plants which are resistant, or have been made resistant by recombinant means, to the phytotoxic effects of the herbicides.
  • nucleic acid molecules which allow mutagenesis or sequence alteration by recombination of DNA sequences can be introduced into plasmids.
  • base exchanges remove parts of sequences or add natural or synthetic sequences.
  • adapters or linkers may be added to the fragments.
  • the generation of plant cells with a reduced activity of a gene product can be achieved by expressing at least one corresponding antisense RNA, a sense RNA for achieving a cosuppression effect, or by expressing at least one suitably constructed ribozyme which specifically cleaves transcripts of the abovementioned gene product.
  • DNA molecules which encompass the entire coding sequence of a gene product inclusive of any flanking sequences which may be present and also DNA molecules which only encompass portions of the coding sequence, in which case it is necessary for these portions to be long enough to have an antisense effect in the cells.
  • DNA sequences which have a high degree of homology to the coding sequences of a gene product but are not completely identical to them When expressing nucleic acid molecules in plants, the protein synthesized may be localized in any desired compartment of the plant cell. However, to achieve localization in a particular compartment, it is possible, for example, to join the coding region to DNA sequences which ensure localization in a particular compartment. Such sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227).
  • the nucleic acid molecules can also be expressed in the organelles of the plant cells.
  • the transgenic plant cells can be regenerated by known techniques to give rise to entire plants.
  • the transgenic plants may be plants of any desired plant species, i.e. not only monocotyledonous but also dicotyledonous plants.
  • the compounds of general formula (I) in transgenic crops which are resistant to growth regulators such as, for example, dicamba, or to herbicides which inhibit essential plant enzymes, for example acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD), or to herbicides from the group of the sulfonylureas, glyphosate, glufosinate or benzoylisoxazoles and analogous active compounds.
  • growth regulators such as, for example, dicamba, or to herbicides which inhibit essential plant enzymes, for example acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD), or to herbicides from the group of the sulfonylureas, glyphosate, glufosinate or benzoylisoxazoles and analog
  • the active compounds of the invention are employed in transgenic crops, not only do the effects toward harmful plants observed in other crops occur, but frequently also effects which are specific to application in the particular transgenic crop, for example an altered or specifically widened spectrum of weeds which can be controlled, altered application rates which can be used for the application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and influencing of growth and yield of the transgenic crop plants.
  • the invention therefore also relates to the use of the compounds of the general formula (I) according to the invention and/or their salts as herbicides for controlling harmful plants in crops of useful plants or ornamentals, optionally in transgenic crop plants.
  • cereals here preferably corn, wheat, barley, rye, oats, millet or rice, by the pre- or post-emergence method.
  • the use according to the invention for the control of harmful plants or for growth regulation of plants also includes the case in which the active compound of the general formula (I) or its salt is not formed from a precursor substance (“prodrug”) until after application on the plant, in the plant or in the soil.
  • the invention also provides for the use of one or more compounds of the general formula (I) or salts thereof or of a composition according to the invention (as defined below) (in a method) for controlling harmful plants or for regulating the growth of plants which comprises applying an effective amount of one or more compounds of the general formula (I) or salts thereof onto the plants (harmful plants, if appropriate together with the useful plants), plant seeds, the soil in which or on which the plants grow or the area under cultivation.
  • the invention also provides a herbicidal and/or plant growth-regulating composition, characterized in that the composition comprises
  • one or more further agrochemically active substances preferably selected from the group consisting of insecticides, acaricides, nematicides, further herbicides (i.e. those not corresponding to the general formula (I) defined above), fungicides, safeners, fertilizers and/or further growth regulators,
  • component (i) of a composition according to the invention are preferably selected from the group of substances mentioned in "The Pesticide Manual”, 16th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2012.
  • a herbicidal or plant growth-regulating composition according to the invention comprises preferably one, two, three or more formulation auxiliaries (ii) customary in crop protection selected from the group consisting of surfactants, emulsifiers, dispersants, film-formers, thickeners, inorganic salts, dusting agents, carriers solid at 25 °C and 1013 mbar, preferably adsorbent granulated inert materials, wetting agents, antioxidants, stabilizers, buffer substances, antifoam agents, water, organic solvents, preferably organic solvents miscible with water in any ratio at 25 °C and 1013 mbar.
  • formulation auxiliaries customary in crop protection selected from the group consisting of surfactants, emulsifiers, dispersants, film-formers, thickeners, inorganic salts, dusting agents, carriers solid at 25 °C and 1013 mbar, preferably adsorbent granulated inert materials, wetting agents, antioxidants, stabilizers, buffer
  • the compounds of general formula (I) according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusting products or granules in the customary formulations.
  • the invention therefore also provides herbicidal and plant growth-regulating compositions which comprise compounds of the general formula (I) and/or salts thereof.
  • the compounds of the general formula (I) and/or salts thereof can be formulated in various ways according to which biological and/or physicochemical parameters are required.
  • Possible formulations include, for example: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in- water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), dispersions based on oil or water, oil-miscible solutions, capsule suspensions (CS), dusting products (DP), dressings, granules for scattering and soil application, granules (GR) in the form of microgranules, spray granules, absorption and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.
  • WP wettable powders
  • Wettable powders are preparations which can be dispersed uniformly in water and, in addition to the active compound, apart from a diluent or inert substance, also comprise surfactants of the ionic and/or nonionic type (wetting agents, dispersants), for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthylmethane-6,6'- disulfonate, sodium dibutylnaphthalenesulfonate or else sodium oleoylmethyltaurate.
  • surfactants of the ionic and/or nonionic type for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxye
  • the herbicidally active compounds are finely ground, for example in customary apparatuses such as hammer mills, blower mills and air-jet mills, and simultaneously or subsequently mixed with the formulation auxiliaries.
  • Emulsifiable concentrates are produced by dissolving the active compound in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene, or else relatively high-boiling aromatics or hydrocarbons or mixtures of the organic solvents, with addition of one or more ionic and/or nonionic surfactants (emulsifiers).
  • emulsifiers which may be used are: calcium alkylarylsulfonates such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, for example sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, for example polyoxyethylene sorbitan fatty acid esters.
  • calcium alkylarylsulfonates such as calcium dodecylbenzenesulfonate
  • nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, for example sorbitan fatty acid est
  • Dusting products are obtained by grinding the active compound with finely distributed solids, for example talc, natural clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • finely distributed solids for example talc, natural clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • Suspension concentrates may be water- or oil-based. They may be prepared, for example, by wet grinding by means of commercial bead mills and optional addition of surfactants as have, for example, already been listed above for the other formulation types.
  • Emulsions for example oil-in- water emulsions (EW)
  • EW oil-in- water emulsions
  • Granules can be produced either by spraying the active compound onto adsorptive granular inert material or by applying active compound concentrates to the surface of carriers, such as sand, kaolinites or granular inert material, by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate or else mineral oils.
  • active compounds can also be granulated in the manner customary for the production of fertilizer granules - if desired as a mixture with fertilizers.
  • Water-dispersible granules are produced generally by the customary processes such as spray-drying, fluidized-bed granulation, pan granulation, mixing with high-speed mixers and extrusion without solid inert material.
  • the agrochemical preparations, preferably herbicidal or plant growth-regulating compositions, of the present invention preferably comprise a total amount of from 0.1 to 99% by weight, preferably 0.5 to 95% by weight, particularly preferably 1 to 90% by weight, especially preferably 2 to 80% by weight, of active compounds of the general formula (I) and their salts.
  • the active compound concentration is, for example, about 10 to 90% by weight, the remainder to 100% by weight consisting of customary formulation constituents. In emulsifiable concentrates, the active compound concentration may be about 1% to 90% and preferably 5% to 80% by weight.
  • Formulations in the form of dusts comprise 1% to 30% by weight of active compound, preferably usually 5% to 20% by weight of active compound; sprayable solutions contain about 0.05% to 80% by weight, preferably 2% to 50% by weight of active compound.
  • the active compound content depends partially on whether the active compound is in liquid or solid form and on which granulation auxiliaries, fillers, etc., are used. In the water-dispersible granules, the content of active compound is, for example, between 1% and 95% by weight, preferably between 10% and 80% by weight.
  • the active compound formulations mentioned optionally comprise the respective customary stickers, wetters, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and agents which influence the pH and the viscosity.
  • formulation auxiliaries are described inter alia in “Chemistry and Technology of Agrochemical Formulations”, ed. D.A. Knowles, Kluwer Academic Publishers (1998).
  • the compounds of the general formula (I) or salts thereof can be used as such or in the form of their preparations (formulations) in a combination with other pesticidally active substances, for example insecticides, acaricides, nematicides, herbicides, fungicides, safeners, fertilizers and/or growth regulators, for example in the form of a finished formulation or of a tank mix.
  • pesticidally active substances for example insecticides, acaricides, nematicides, herbicides, fungicides, safeners, fertilizers and/or growth regulators, for example in the form of a finished formulation or of a tank mix.
  • the combination formulations can be prepared on the basis of the abovementioned formulations, while taking account of the physical properties and stabilities of the active compounds to be combined.
  • Active compounds which can be employed in combination with the compounds of general formula (I) according to the invention in mixture formulations or in a tank mix are, for example, known active compounds based on inhibition of, for example, acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvylshikimate-3-phosphate synthase, glutamine synthetase, p- hydroxyphenylpyruvate dioxygenase, phytoendesaturase, photosystem I, photosystem II, protoporphyrinogen oxidase, as described, for example, in Weed Research 26 (1986) 441-445 or "The Pesticide Manual", 16th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2012 and literature cited therein.
  • the safeners which are used in an antidotically effective amount, reduce the phytotoxic side effects of the herbicides/pesticides employed, for example in economically important crops, such as cereals (wheat, barley, rye, corn, rice, millet), sugarbeet, sugarcane, oilseed rape, cotton and soybeans, preferably cereals.
  • the weight ratios of herbicide (mixture) to safener depend generally on the herbicide application rate and the efficacy of the safener in question and may vary within wide limits, for example in the range from 200:1 to 1:200, preferably 100:1 to 1:100, in particular 20:1 to 1:20.
  • the safeners can be formulated with further herbicides/pesticides and be provided and employed as a finished formulation or tank mix with the herbicides.
  • the herbicide or herbicide/safener formulations present in commercial form are, if appropriate, diluted in a customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules with water. Dust-type preparations, granules for soil application or granules for scattering and sprayable solutions are not normally diluted further with other inert substances prior to application.
  • the application rate of the compounds of the general formula (I) and/or their salts is affected to a certain extent by external conditions such as temperature, humidity, etc.
  • the application rate may vary within wide limits.
  • the total amount of compounds of the general formula (I) and/or their salts is preferably in the range from 0.001 to 10.0 kg/ha, with preference in the range from 0.005 to 5 kg/ha, more preferably in the range from 0.01 to 1.5 kg/ha, in particular preferably in the range from 0.05 to 1 kg/ha. This applies both to the pre-emergence and the post-emergence application.
  • the total application rate is preferably in the range of from 0.001 to 2 kg/ha, preferably in the range of from 0.005 to 1 kg/ha, in particular in the range of from 10 to 500 g/ha, very particularly in the range from 20 to 250 g/ha. This applies both to the pre emergence and the post-emergence application.
  • the application as culm stabilizer may take place at various stages of the growth of the plants. Preferred is, for example, the application after the tilling phase, at the beginning of the longitudinal growth.
  • application as plant growth regulator is also possible by treating the seed, which includes various techniques for dressing and coating seed.
  • the application rate depends on the particular techniques and can be determined in preliminary tests.
  • Active compounds which can be employed in combination with the compounds of the general formula (I) according to the invention in compositions according to the invention are, for example, known active compounds which are based on the inhibition of, for example, acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvylshikimate-3-phosphate synthase, glutamine synthetase, p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase, photosystem I, photosystem II, protoporphyrinogen oxidase, as are described in, for example, Weed Research 26 (1986) 441-445 or "The Pesticide Manual", 16th edition, The British Crop Protection Council and the Royal Soc.
  • herbicides or plant growth regulators which can be combined with the compounds according to the invention are, for example, the following active compounds, where the compounds are designated either with the "common name” in accordance with the International Organization for Standardization (ISO) or with the chemical name or with the code number. They always encompass all of the application forms such as, for example, acids, salts, esters and also all isomeric forms such as stereoisomers and optical isomers, even if not explicitly mentioned.
  • herbicidal mixing partners are:
  • dicamba-biproamine dicamba-N,N-Bis(3-aminopropyl)methylamine, dicamba-butotyl, dicamba-choline, dicamba-diglycolamine, dicamba-dimethylammonium, dicamba- diethanolaminemmonium, dicamba-diethylammonium, dicamba-isopropylammonium, dicamba-methyl, dicamba-monoethanolaminedicamba-olamine, dicamba-potassium, dicamba-sodium, dicamba- triethanolamine, dichlobenil, 2-(2,4-dichlorobenzyl)-4, 4-dimethyl- l,2-oxazolidin-3-one, 2-(2,5- dichlorobenzyl)-4, 4-dimethyl- 1 ,2-oxazolidin-3-one, dichlorprop, dichlorprop-butotyl, dichlroprop- dimethylammonium, dichhlorprop-etex
  • plant growth regulators as possible mixing partners are:
  • chitosan molecules [(CsHnNO ⁇ n , CAS No. 9012-76-4]), chitinous compounds, chlormequat chloride, cloprop, cyclanilide, 3-(Cycloprop-l- enyl)propionic acid, daminozide, dazomet, dazomet-sodium, n-decanol, dikegulac, dikegulac-sodium, endothal, endothal-dipotassium, -disodium, and mono(N,N-dimethylalkylammonium), ethephon, flumetralin, flurenol, flurenol-butyl, flurenol-methyl, flurprimidol, forchlorfenuron, gibberellic acid, inabenfide, indol-3-acetic acid (IAA), 4-indol-3-ylbutyric acid, isoprothi
  • LCO lipo-chitooligosaccharides
  • Nod symbiotic nodulation
  • Myc factors consist of an oligosaccharide backbone of ⁇ -l,4-linked N-acetyl-D-glucosamine (“GlcNAc”) residues with an N-linked fatty acyl chain condensed at the non-reducing end.
  • LCOs differ in the number of GlcNAc residues in the backbone, in the length and degree of saturation of the fatty acyl chain and in the substitutions of reducing and non-reducing sugar residues), linoleic acid or derivatives thereof, linolenic acid or derivatives thereof, maleic hydrazide, mepiquat chloride, mepiquat pentaborate, 1-methylcyclopropene, 3’-methyl abscisic acid, 2-(1-naphthyl)acetamide, 1-naphthylacetic acid, 2- naphthyloxyacetic acid, nitrophenolate-mixture, 4-Oxo-4[(2-phenylethyl)amino]butyric acid, paclobutrazol, 4-phenylbutyric acid, N-phenylphthalamic acid, prohexadione, prohexadione-calcium, prohydrojasmon, salicylic acid, salicylic
  • Suitable combination partners for the compounds of the general formula (I) according to the invention also include, for example, the following safeners: S1) Compounds from the group of heterocyclic carboxylic acid derivatives: S1 a ) Compounds of the dichlorophenylpyrazoline-3-carboxylic acid type (S1 a ), preferably compounds such as 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic acid, ethyl 1- (2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate (S1-1) ("mefenpyr-diethyl”), and related compounds as described in WO-A-91/07874; S1 b ) Derivatives of dichlorophenylpyrazolecarboxylic acid (S1 b ), preferably compounds such as ethyl 1-(2,4-dichlor
  • S2 a Compounds from the group of the 8-quinolinoxy derivatives (S2): S2 a ) Compounds of the 8-quinolinoxyacetic acid type (S2 a ), preferably 1-methylhexyl (5-chloro-8- quinolinoxy)acetate ("cloquintocet-mexyl") (S2-1), 1,3-dimethylbut-1-yl (5-chloro-8- quinolinoxy)acetate (S2-2), 4-allyloxybutyl (5-chloro-8-quinolinoxy)acetate (S2-3), 1- allyloxyprop-2-yl (5-chloro-8-quinolinoxy)acetate (S2-4), ethyl (5-chloro-8-quinolinoxy)acetate (S2-5), methyl 5-chloro-8-quinolinoxyacetate (S2-6), allyl (5-chloro-8-quinolinoxy)acetate (S2- 7), 2-(2-propylideneiminoxy)-1-eth
  • S3 Active compounds of the dichloroacetamide type (S3), which are frequently used as pre- emergence safeners (soil-acting safeners), for example "dichlormid” (N,N-diallyl-2,2-dichloroacetamide) (S3-1), "R-29148” (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) from Stauffer (S3-2), "R-28725" (3-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine) from Stauffer (S3-3), "benoxacor” (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4), "PPG-1292” (N-allyl-N-[(1,3-dioxolan-2-yl)methyl]dichloroacetamide) from PPG Industries (S3-5), "DKA-24" (N-ally
  • S4 a N-Acylsulfonamides of the formula (S4 a ) and salts thereof, as described in WO-A-97/45016, in which R A 1 is (C 1 -C 6 )-alkyl, (C 3 -C 6 )-cycloalkyl, where the 2 latter radicals are substituted by v A substituents from the group of halogen, (C 1 -C 4 )-alkoxy, (C 1 -C 6 )-haloalkoxy and (C 1 -C 4 )- alkylthio and, in the case of cyclic radicals, also by (C 1 -C 4 )-alkyl and (C 1 -C 4 )-haloalkyl; R A 2 is halogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy,
  • Active compounds from the class of the hydroxyaromatics and the aromatic-aliphatic carboxylic acid derivatives (S5) for example ethyl 3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4- hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicyclic acid, 2-hydroxycinnamic acid, 2,4-dichlorocinnamic acid, as described in WO-A-2004/084631, WO-A-2005/015994, WO-A-2005/016001.
  • S6 Active compounds from the class of the 1,2-dihydroquinoxalin-2-ones (S6), for example 1- methyl-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one, 1-methyl-3-(2-thienyl)-1,2- dihydroquinoxaline-2-thione, 1-(2-aminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one hydrochloride, 1-(2-methylsulfonylaminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one, as described in WO-A-2005/112630.
  • S7 Compounds from the class of the diphenylmethoxyacetic acid derivatives (S7), e.g. methyl diphenylmethoxyacetate (CAS Reg. No.41858-19-9) (S7-1), ethyl diphenylmethoxyacetate or diphenylmethoxyacetic acid, as described in WO-A-98/38856.
  • S7 diphenylmethoxyacetic acid derivatives
  • S9 active compounds from the class of the 3-(5-tetrazolylcarbonyl)-2-quinolones (S9), for example 1,2-dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No.219479- 18-2), 1,2-dihydro-4-hydroxy-1-methyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No.
  • R E 1 is halogen, (C 1 -C 4 )-alkyl, methoxy, nitro, cyano, CF 3 , OCF 3 Y E , Z E are independently O or S
  • n E is an integer from 0 to 4
  • R E 2 is (C 1 -C 16 )-alkyl, (C 2 -C 6 )-alkenyl, (C 3 -C 6 )-cycloalkyl, aryl; benzyl, halobenzyl, R E 3 is hydrogen or (Ci-C 6 )-alkyl.
  • SI 1 Active compounds of the oxyimino compound type (SI 1), which are known as seed-dressing agents, for example
  • oxahetrinil ((Z)-l,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile) (SI 1-1), which is known as a seed-dressing safener for millet/sorghum against metolachlor damage,
  • Flufluxofenim (l-(4-chlorophenyl)-2,2,2-trifluoro-l-ethanone 0-(l,3-dioxolan-2- ylmethyl)oxime) (SI 1-2), which is known as a seed-dressing safener for millet/sorghum against metolachlor damage, and
  • CGA-43089 (Z)-cyanomethoxyimino(phenyl)acetonitrile) (SI 1-3), which is known as a seed-dressing safener for millet/sorghum against metolachlor damage.
  • naphthalic anhydride (1,8-naphthalenedicarboxylic anhydride) (S13-1), which is known as a seed-dressing safener for corn against thiocarbamate herbicide damage,
  • flurazole (benzyl 2-chloro-4-trifluoromethyl-l,3-thiazole-5-carboxylate) (S13-3), which is known as a seed-dressing safener for millet/sorghum against alachlor and metolachlor damage,
  • MG 191 (CAS Reg. No. 96420-72-3) (2-dichloromethyl-2-methyl-l,3-dioxolane) (S13-5) from Nitrokemia, which is known as a safener for corn,
  • active compounds which, in addition to herbicidal action against weeds, also have safener action on crop plants such as rice, for example
  • RH 1 is a (Ci-C 6 )-haloalkyl radical
  • R H 2 is hydrogen or halogen
  • RH 3 , RH 4 are each independently hydrogen, (Ci-Ci 6 )-alkyl, (C2-Ci6)-alkenyl or (C2-Ci6)-alkynyl, where each of the 3 latter radicals is unsubstituted or substituted by one or more radicals from the group of halogen, hydroxyl, cyano, (Ci-C4)-alkoxy, (Ci-C4)-haloalkoxy, (Ci- C4)-alkylthio, (C1-C4)-alkylamino, di[(C1-C4)-alkyl]amino, [(C1-C4)-alkoxy]carbonyl, [(C1-C4)-haloalkoxy]carbonyl, (C3-C6)-cycloalkyl which is unsubstituted or substituted, phenyl which is unsubstituted or substituted, and heterocyclyl which is unsubstituted or substituted, or (C 3
  • Preferred safeners in combination with the compounds of the general formula (I) according to the invention and/or salts thereof, in particular with the compounds of the formulae (1-001) to (1-051) and/or salts thereof, are: cloquintocet-mexyl, cyprosulf amide, fenchlorazole-ethyl, isoxadifen-ethyl, mefenpyr- diethyl, fenclorim, cumyluron, S4-1 and S4-5, and particularly preferred safeners are: cloquintocet- mexyl, cyprosulfamide, isoxadifen-ethyl and mefenpyr-diethyl.
  • ABUTH Abutilon theophrasti
  • ECHCG Echinochloa crus-galli
  • KCHSC Kochia scoparia
  • MATIN Matricaria inodora
  • VERPE Veronica persica
  • Tables A1 to A12 show the effects of selected compounds of the general formula (I) according to Table 1 on various harmful plants and an application rate corresponding to 1280 g/ha obtained by the experimental procedure mentioned above.
  • Table A1 shows the effects of selected compounds of the general formula (I) according to Table 1 on various harmful plants and an application rate corresponding to 1280 g/ha obtained by the experimental procedure mentioned above.
  • Test plants were sown in plastic pots (double sowings with one species of mono- and one species of dicotyledonous weed plants per pot), in sandy loam, covered with soil and grown under controlled growth conditions. 2 to 3 weeks after sowing, the test plants were sprayed in the single-leaf stage.
  • the compounds according to the invention formulated in the form of wettable powders (WP) or as emulsifiable concentrates (EC), were sprayed onto the green plant parts as an aqueous suspension or as an emulsion, with the addition of 0.5% of an additive, at an application rate of 600 litres of water per hectare (converted).
  • WP wettable powders
  • EC emulsifiable concentrates
  • Tables Cl to Cl 1 below show the effects of selected compounds of the general formula (I) according to Table 1 on various harmful plants using an application rate corresponding to 320 g/ha obtained by the experimental procedure mentioned above.
  • various compounds of the general formula (I) according to the invention have very good herbicidal pre-emergence efficacy against a broad spectrum of harmful mono- and dicotyledonous plants such as Abutilon theophrasti, Alopecurus myosuroides, Amaranthus retroflexus, Echinochloa crus-galli, Kochia scoparia, Lolium rigidum, Matricaria inodora, Poa annua, Setaria viridis, Stellaria media and Veronica persica at an application rate of 320 g of active ingredient per hectare.
  • harmful mono- and dicotyledonous plants such as Abutilon theophrasti, Alopecurus myosuroides, Amaranthus retroflexus, Echinochloa crus-galli, Kochia scoparia, Lolium rigidum, Matricaria inodora, Poa annua, Setaria viridis, Stellaria media and Veronica persica at an application rate of 320 g of active ingredient per hectare.
  • Tables D1 to D11 below show the effects of selected compounds of the general formula (I) according to Table 1 on various harmful plants using an application rate corresponding to 320 g/ha obtained by the experimental procedure mentioned above.
  • Seeds of mono- and dicotyledonous weed plants were sown in plastic pots (double sowings with one species of mono- and one species of dicotyledonous weed plants per pot), in sandy loam, and covered with soil.
  • the compounds according to the invention formulated in the form of wettable powders (WP) or as emulsifiable concentrates (EC), were applied to the surface of the covering soil as aqueous suspension or emulsion, with the addition of 0.5% of an additive, at an application rate of 600 litres of water per hectare (converted). Following treatment, the pots were placed in a greenhouse and kept under optimum growth conditions for the test plants. The visual grading of the damage to the test plants was carried out after ca. 3 weeks in comparison to untreated controls
  • Table El shows the effects of a selected compound of the general formula (I) according to Table 1 on Lolium rigidum and Poa annua in comparison with a comparative compound bearing a different R 2 substituent using application rates corresponding to 1280, 320 and 80 g/ha obtained by the experimental procedure mentioned above.
  • the compound of the general formula (I) provides surprisingly improved herbicidal pre-emergence efficacy against Lolium rigidum and Poa annua at application rates of 1280, 320 and 80 g of active ingredient per hectare.
  • Table FI shows the effects of a selected compound of the general formula (I) according to Table 1 on Lolium rigidum and Poa annua in comparison with a comparative compound bearing a different R 2 substituent using application rates corresponding to 1280, 320 and 80 g/ha obtained by the experimental procedure mentioned above.
  • the compound of the general formula (I) provides surprisingly improved herbicidal post-emergence efficacy against Lolium rigidum and Poa annua at application rates of 1280, 320 and 80 g of active ingredient per hectare.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne des 1,2,4-thiadiazoles substitués, leurs sels et leur utilisation en tant que substances actives herbicides. L'invention concerne des 1,2,4-thiadiazoles substitués de formule générale (I) ou des sels de ceux-ci, les radicaux dans la formule générale (I) correspondant aux définitions données dans la description, et leur utilisation comme herbicides, en particulier pour lutter contre les mauvaises herbes à larges feuilles et/ou les graminées adventices dans des cultures de plantes utiles et/ou comme régulateurs de croissance de plantes pour influencer la croissance de cultures de plantes utiles.
PCT/EP2022/056653 2021-03-19 2022-03-15 1,2,4-thiadiazoles substitués, leurs sels et leur utilisation comme substances actives herbicides WO2022194843A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP21163740.0 2021-03-19
EP21163740 2021-03-19

Publications (1)

Publication Number Publication Date
WO2022194843A1 true WO2022194843A1 (fr) 2022-09-22

Family

ID=75111511

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2022/056653 WO2022194843A1 (fr) 2021-03-19 2022-03-15 1,2,4-thiadiazoles substitués, leurs sels et leur utilisation comme substances actives herbicides

Country Status (2)

Country Link
AR (1) AR125154A1 (fr)
WO (1) WO2022194843A1 (fr)

Citations (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2154852A1 (en) 1970-11-27 1972-06-15 Makhteshim Beer Sheva Chemical Works Ltd, Beer Sheva (Israel) 5-substd amino-3-isopropyl-1,2,4-thiadiazoles - pesticides and herbici
EP0049071A1 (fr) 1980-09-16 1982-04-07 Eli Lilly And Company Dérivés N-aryl benzamides
US4337081A (en) 1979-01-23 1982-06-29 Olin Corporation 5-Amido-3-trihalomethyl-1,2,4-thiadiazoles and their use as herbicides
US4343945A (en) 1979-01-23 1982-08-10 Olin Corporation 5-Benzamido-3-trichloromethyl-1,2,4-thiadiazoles and their use as herbicides, fungicides and insecticides
EP0086750A2 (fr) 1982-02-17 1983-08-24 Ciba-Geigy Ag Utilisation de dérivés de la quinoléine pour la protection de plantes cultivables
EP0094349A2 (fr) 1982-05-07 1983-11-16 Ciba-Geigy Ag Utilisation de dérivés de quinoléine pour protéger des plantes cultivées
US4416683A (en) 1980-09-16 1983-11-22 Eli Lilly And Company Benzamides, compositions and agricultural method
US4515625A (en) 1980-09-16 1985-05-07 Eli Lilly And Company Benzamides, compositions and agricultural method
JPS6087254A (ja) 1983-10-19 1985-05-16 Japan Carlit Co Ltd:The 新規尿素化合物及びそれを含有する除草剤
EP0174562A2 (fr) 1984-09-11 1986-03-19 Hoechst Aktiengesellschaft Agents pour la protection de plantes basés sur des dérivés de 1,2,4- briazole ainsi que dérivés 1,2,4-triazole
EP0191736A2 (fr) 1985-02-14 1986-08-20 Ciba-Geigy Ag Utilisation de dérivés de la quinoléine pour la protection de plantes cultivables
US4636243A (en) 1980-09-16 1987-01-13 Eli Lilly And Company Benzamides, compositions and agricultural method
EP0268554A2 (fr) 1986-10-22 1988-05-25 Ciba-Geigy Ag Dérivés d'acide diphényl-1,5-pyrazol-3-carbonique pour la protection de plantes de culture
EP0269806A1 (fr) 1986-10-04 1988-06-08 Hoechst Aktiengesellschaft Dérivés d'acide phénylpyrazolcarbonique, leur préparation et leur utilisation comme agents régulateurs de croissance des plantes et antidote
US4801718A (en) 1980-09-16 1989-01-31 Eli Lilly And Company Thiaiazolyl benzamides
EP0346620A1 (fr) 1988-05-20 1989-12-20 Hoechst Aktiengesellschaft Agents phytoprotecteurs contenant des dérivés du 1,2,4-triazole ainsi que dérivés du 1,2,4-triazole
EP0365484A1 (fr) 1988-10-20 1990-04-25 Ciba-Geigy Ag Sulfamoylphénylurées
WO1991007874A1 (fr) 1989-11-30 1991-06-13 Hoechst Aktiengesellschaft Pyrazoline pour la protection de plantes cultivees contre les herbicides
WO1991008202A1 (fr) 1989-11-25 1991-06-13 Hoechst Aktiengesellschaft Isoxazolines, procede de preparation et application comme produits phytosanitaires
EP0492366A2 (fr) 1990-12-21 1992-07-01 Hoechst Schering AgrEvo GmbH Nouveaux dérivés de chloro-5-quinoline-8-acide oxyalkanecarboniques, procédé pour leur préparation et leur utilisation comme antidote d'herbicides
EP0582198A2 (fr) 1992-08-01 1994-02-09 Hoechst Schering AgrEvo GmbH Composés (hétéro-)aryliques substitués, procédé pour leur préparation, compositions les contenant et leur utilisation comme agents de protection
WO1995007897A1 (fr) 1993-09-16 1995-03-23 Hoechst Schering Agrevo Gmbh Isoxazolines substituees, leur procede de preparation, agents les contenant et leur utilisation comme reducteurs de phytotoxicite
DE19601139A1 (de) 1996-01-15 1997-07-17 Bayer Ag Acylierte 5-Amino-1,2,4-thiadiazole
WO1997045016A1 (fr) 1996-05-29 1997-12-04 Hoechst Schering Agrevo Gmbh Nouveaux n-acylsulfonamides, nouveaux melanges d'herbicides et d'antidotes et leur utilisation
WO1998013361A1 (fr) 1996-09-26 1998-04-02 Novartis Ag Composition herbicide
WO1998027049A1 (fr) 1996-12-19 1998-06-25 Hoechst Schering Agrevo Gmbh Nouveaux derives d'acide 2-fluoroacrylique, nouveaux melanges d'herbicides et d'antidotes et leur utilisation
WO1998038856A1 (fr) 1997-03-04 1998-09-11 Zeneca Limited Compositions pour proteger du riz contre l'acetochlore
WO1999000020A1 (fr) 1997-06-27 1999-01-07 Hoechst Schering Agrevo Gmbh 3-(5-tetrazolylcarbonyle)-2-quinolones et produits phytosanitaires pour plantes utiles les contenant
WO1999016744A1 (fr) 1997-09-29 1999-04-08 Aventis Cropscience Gmbh Amides d'acide benzoique d'acylsulfamoyle, agents phytosanitaires les contenant et procede permettant de les preparer
WO2001036415A1 (fr) 1999-11-18 2001-05-25 Novartis Ag Composes pesticides aminoheterocyclamide
WO2001040206A1 (fr) 1999-11-29 2001-06-07 Novartis Ag N-heteroaryl alpha-alkoximino-carboxamides pesticides
WO2001040223A2 (fr) 1999-12-02 2001-06-07 Novartis Ag Composes organiques
WO2001046165A2 (fr) 1999-12-16 2001-06-28 Novartis Ag Composes organiques
WO2002034048A1 (fr) 2000-10-23 2002-05-02 Syngenta Participations Ag Compositions agrochimiques avec des phytoprotecteurs a base de quinoline
WO2004084631A1 (fr) 2003-03-26 2004-10-07 Bayer Cropscience Gmbh Utilisation de composés aromatiques hydroxy comme phytoprotecteurs
WO2005016001A1 (fr) 2003-08-05 2005-02-24 Bayer Cropscience Gmbh Agents phytoprotecteurs a base de derives d'acide carboxylique aromatiques-aliphatiques
WO2005015994A1 (fr) 2003-08-05 2005-02-24 Bayer Cropscience Gmbh Utilisation d'aromates hydroxy comme phytoprotecteurs
WO2005112630A1 (fr) 2004-05-12 2005-12-01 Bayer Cropscience Gmbh Derives de quinoxalin-2-one, phytoprotecteurs pour plantes utiles contenant ces derives, procede de production et utilisation desdits derives
WO2007023764A1 (fr) 2005-08-26 2007-03-01 Kumiai Chemical Industry Co., Ltd. Agent servant à réduire les effets nocifs d’un herbicide et composition d’herbicide ayant des effets nocifs réduits
WO2007023719A1 (fr) 2005-08-22 2007-03-01 Kumiai Chemical Industry Co., Ltd. Agent servant à réduire l'attaque chimique et composition herbicide produisant une attaque chimique réduite
WO2008131860A2 (fr) 2007-04-30 2008-11-06 Bayer Cropscience Ag Pyridone-carboxamides, phytoprotecteurs contenant ces composés, procédés pour leur production et leur utilisation
WO2008131861A1 (fr) 2007-04-30 2008-11-06 Bayer Cropscience Ag Utilisation de pyridin-2-oxy-3-carbonamides comme phytoprotecteurs
CN101838227A (zh) 2010-04-30 2010-09-22 孙德群 一种苯甲酰胺类除草剂的安全剂
WO2011035874A1 (fr) * 2009-09-25 2011-03-31 Bayer Cropscience Ag N-(1,2,5-oxadiazol-3-yl) benzamides et leur utilisation comme herbicide
WO2015123133A1 (fr) 2014-02-14 2015-08-20 Inception 2, Inc. Composés à base de pyrazolone et leurs utilisations
WO2017005717A1 (fr) 2015-07-06 2017-01-12 Bayer Cropscience Aktiengesellschaft Composés hétérocycliques utilisés en tant que pesticides
WO2018108791A1 (fr) 2016-12-16 2018-06-21 Bayer Cropscience Aktiengesellschaft Dérivés de thiadiazole utilisés en tant que pesticides
US20190233382A1 (en) 2016-10-20 2019-08-01 Bayer Cropscience Aktiengesellschaft Method for producing 3-alkylsulfanyl-2-chloro-n-(1-alkyl-1h-tetrazol-5-yl)-4-trifluoromethyl-benzamides

Patent Citations (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2154852A1 (en) 1970-11-27 1972-06-15 Makhteshim Beer Sheva Chemical Works Ltd, Beer Sheva (Israel) 5-substd amino-3-isopropyl-1,2,4-thiadiazoles - pesticides and herbici
US4343945A (en) 1979-01-23 1982-08-10 Olin Corporation 5-Benzamido-3-trichloromethyl-1,2,4-thiadiazoles and their use as herbicides, fungicides and insecticides
US4337081A (en) 1979-01-23 1982-06-29 Olin Corporation 5-Amido-3-trihalomethyl-1,2,4-thiadiazoles and their use as herbicides
US4416683A (en) 1980-09-16 1983-11-22 Eli Lilly And Company Benzamides, compositions and agricultural method
US4801718A (en) 1980-09-16 1989-01-31 Eli Lilly And Company Thiaiazolyl benzamides
US4515625A (en) 1980-09-16 1985-05-07 Eli Lilly And Company Benzamides, compositions and agricultural method
US4636243A (en) 1980-09-16 1987-01-13 Eli Lilly And Company Benzamides, compositions and agricultural method
EP0049071A1 (fr) 1980-09-16 1982-04-07 Eli Lilly And Company Dérivés N-aryl benzamides
EP0086750A2 (fr) 1982-02-17 1983-08-24 Ciba-Geigy Ag Utilisation de dérivés de la quinoléine pour la protection de plantes cultivables
EP0094349A2 (fr) 1982-05-07 1983-11-16 Ciba-Geigy Ag Utilisation de dérivés de quinoléine pour protéger des plantes cultivées
JPS6087254A (ja) 1983-10-19 1985-05-16 Japan Carlit Co Ltd:The 新規尿素化合物及びそれを含有する除草剤
EP0174562A2 (fr) 1984-09-11 1986-03-19 Hoechst Aktiengesellschaft Agents pour la protection de plantes basés sur des dérivés de 1,2,4- briazole ainsi que dérivés 1,2,4-triazole
EP0191736A2 (fr) 1985-02-14 1986-08-20 Ciba-Geigy Ag Utilisation de dérivés de la quinoléine pour la protection de plantes cultivables
EP0269806A1 (fr) 1986-10-04 1988-06-08 Hoechst Aktiengesellschaft Dérivés d'acide phénylpyrazolcarbonique, leur préparation et leur utilisation comme agents régulateurs de croissance des plantes et antidote
EP0268554A2 (fr) 1986-10-22 1988-05-25 Ciba-Geigy Ag Dérivés d'acide diphényl-1,5-pyrazol-3-carbonique pour la protection de plantes de culture
EP0346620A1 (fr) 1988-05-20 1989-12-20 Hoechst Aktiengesellschaft Agents phytoprotecteurs contenant des dérivés du 1,2,4-triazole ainsi que dérivés du 1,2,4-triazole
EP0365484A1 (fr) 1988-10-20 1990-04-25 Ciba-Geigy Ag Sulfamoylphénylurées
WO1991008202A1 (fr) 1989-11-25 1991-06-13 Hoechst Aktiengesellschaft Isoxazolines, procede de preparation et application comme produits phytosanitaires
WO1991007874A1 (fr) 1989-11-30 1991-06-13 Hoechst Aktiengesellschaft Pyrazoline pour la protection de plantes cultivees contre les herbicides
EP0492366A2 (fr) 1990-12-21 1992-07-01 Hoechst Schering AgrEvo GmbH Nouveaux dérivés de chloro-5-quinoline-8-acide oxyalkanecarboniques, procédé pour leur préparation et leur utilisation comme antidote d'herbicides
EP0582198A2 (fr) 1992-08-01 1994-02-09 Hoechst Schering AgrEvo GmbH Composés (hétéro-)aryliques substitués, procédé pour leur préparation, compositions les contenant et leur utilisation comme agents de protection
WO1995007897A1 (fr) 1993-09-16 1995-03-23 Hoechst Schering Agrevo Gmbh Isoxazolines substituees, leur procede de preparation, agents les contenant et leur utilisation comme reducteurs de phytotoxicite
DE19601139A1 (de) 1996-01-15 1997-07-17 Bayer Ag Acylierte 5-Amino-1,2,4-thiadiazole
WO1997045016A1 (fr) 1996-05-29 1997-12-04 Hoechst Schering Agrevo Gmbh Nouveaux n-acylsulfonamides, nouveaux melanges d'herbicides et d'antidotes et leur utilisation
WO1998013361A1 (fr) 1996-09-26 1998-04-02 Novartis Ag Composition herbicide
WO1998027049A1 (fr) 1996-12-19 1998-06-25 Hoechst Schering Agrevo Gmbh Nouveaux derives d'acide 2-fluoroacrylique, nouveaux melanges d'herbicides et d'antidotes et leur utilisation
WO1998038856A1 (fr) 1997-03-04 1998-09-11 Zeneca Limited Compositions pour proteger du riz contre l'acetochlore
WO1999000020A1 (fr) 1997-06-27 1999-01-07 Hoechst Schering Agrevo Gmbh 3-(5-tetrazolylcarbonyle)-2-quinolones et produits phytosanitaires pour plantes utiles les contenant
WO1999016744A1 (fr) 1997-09-29 1999-04-08 Aventis Cropscience Gmbh Amides d'acide benzoique d'acylsulfamoyle, agents phytosanitaires les contenant et procede permettant de les preparer
WO2001036415A1 (fr) 1999-11-18 2001-05-25 Novartis Ag Composes pesticides aminoheterocyclamide
WO2001040206A1 (fr) 1999-11-29 2001-06-07 Novartis Ag N-heteroaryl alpha-alkoximino-carboxamides pesticides
WO2001040223A2 (fr) 1999-12-02 2001-06-07 Novartis Ag Composes organiques
WO2001046165A2 (fr) 1999-12-16 2001-06-28 Novartis Ag Composes organiques
WO2002034048A1 (fr) 2000-10-23 2002-05-02 Syngenta Participations Ag Compositions agrochimiques avec des phytoprotecteurs a base de quinoline
WO2004084631A1 (fr) 2003-03-26 2004-10-07 Bayer Cropscience Gmbh Utilisation de composés aromatiques hydroxy comme phytoprotecteurs
WO2005016001A1 (fr) 2003-08-05 2005-02-24 Bayer Cropscience Gmbh Agents phytoprotecteurs a base de derives d'acide carboxylique aromatiques-aliphatiques
WO2005015994A1 (fr) 2003-08-05 2005-02-24 Bayer Cropscience Gmbh Utilisation d'aromates hydroxy comme phytoprotecteurs
WO2005112630A1 (fr) 2004-05-12 2005-12-01 Bayer Cropscience Gmbh Derives de quinoxalin-2-one, phytoprotecteurs pour plantes utiles contenant ces derives, procede de production et utilisation desdits derives
WO2007023719A1 (fr) 2005-08-22 2007-03-01 Kumiai Chemical Industry Co., Ltd. Agent servant à réduire l'attaque chimique et composition herbicide produisant une attaque chimique réduite
WO2007023764A1 (fr) 2005-08-26 2007-03-01 Kumiai Chemical Industry Co., Ltd. Agent servant à réduire les effets nocifs d’un herbicide et composition d’herbicide ayant des effets nocifs réduits
WO2008131860A2 (fr) 2007-04-30 2008-11-06 Bayer Cropscience Ag Pyridone-carboxamides, phytoprotecteurs contenant ces composés, procédés pour leur production et leur utilisation
WO2008131861A1 (fr) 2007-04-30 2008-11-06 Bayer Cropscience Ag Utilisation de pyridin-2-oxy-3-carbonamides comme phytoprotecteurs
WO2011035874A1 (fr) * 2009-09-25 2011-03-31 Bayer Cropscience Ag N-(1,2,5-oxadiazol-3-yl) benzamides et leur utilisation comme herbicide
CN101838227A (zh) 2010-04-30 2010-09-22 孙德群 一种苯甲酰胺类除草剂的安全剂
WO2015123133A1 (fr) 2014-02-14 2015-08-20 Inception 2, Inc. Composés à base de pyrazolone et leurs utilisations
WO2017005717A1 (fr) 2015-07-06 2017-01-12 Bayer Cropscience Aktiengesellschaft Composés hétérocycliques utilisés en tant que pesticides
US20190233382A1 (en) 2016-10-20 2019-08-01 Bayer Cropscience Aktiengesellschaft Method for producing 3-alkylsulfanyl-2-chloro-n-(1-alkyl-1h-tetrazol-5-yl)-4-trifluoromethyl-benzamides
WO2018108791A1 (fr) 2016-12-16 2018-06-21 Bayer Cropscience Aktiengesellschaft Dérivés de thiadiazole utilisés en tant que pesticides

Non-Patent Citations (22)

* Cited by examiner, † Cited by third party
Title
"Chemistry and Technology of Agrochemical Formulations", 1998, KLUWER ACADEMIC PUBLISHERS
"Perry's Chemical Engineer's Handbook", 1973, MCGRAW HILL, pages: 8 - 57
"Spray Drying Handbook", 1979, G. GOODWIN LTD.
"The Pesticide Manual", 2012, THE ROYAL SOC. OF CHEMISTRY
ANGEW. CHEM. INT. ED., vol. 43, 2004, pages 1132 - 1136
BEILSTEIN J. ORG. CHEM., vol. 17, 2021, pages 245 - 272
BRAUN ET AL., EMBO J., vol. 11, 1992, pages 3219 - 3227
CAS , no. 133993-74-5
CHEM. COMMUN., 2008, pages 1100 - 1102
CHEM. SOC. REV., vol. 38, 2009, pages 606 - 631
G.C. KLINGMAN: "Weed Control as a Science", 1961, JOHN WILEY AND SONS, INC., pages: 81 - 96
J. AM. CHEM. SOC., vol. 125, 2003, pages 5616 - 5617
J. AM. CHEM. SOC., vol. 126, 2004, pages 13028 - 13032
J. ORG. CHEM., vol. 73, 2008, pages 8030 - 8032
J. ORG. CHEM., vol. 76, 2011, pages 8036 - 8041
J.D. FREYERS.A. EVANS: "Weed Control Handbook", 1968, BLACKWELL SCIENTIFIC PUBLICATIONS, pages: 101 - 103
J.E. BROWNING: "Agglomeration", CHEMICAL AND ENGINEERING, 1967, pages 147
MCCUTCHEON'S: "Encyclopedia of Surface Active Agents", 1964, CHEM. PUBL. CO. INC.
SCHONFELDT: "Grenzflachenaktive Athylenoxidaddukte", 1976, VERLAGSGESELLSCHAFT
TETRAHEDRON LETT., vol. 47, 2006, pages 5767 - 5769
WATKINSDARLAND BOOKS: "Handbook of Insecticide Dust Diluents and Carriers", 1963, J. WILEY & SONS
WEED RESEARCH, vol. 26, 1986, pages 441 - 445

Also Published As

Publication number Publication date
AR125154A1 (es) 2023-06-14

Similar Documents

Publication Publication Date Title
JP6062528B2 (ja) ５−アミノピリミジン誘導体及び望ましくない植物の成長を防除するためのそれらの使用
JP2023531060A (ja) 置換されているヘテロアリールオキシピリジン類、それらの塩及び除草剤としてのそれらの使用
JP7107962B2 (ja) ２－アミノ－５－オキシアルキル－ピリミジン誘導体および望ましくない植物成長を防除するためのその使用
US12052991B2 (en) Substituted pyridinyloxybenzenes and salts thereof and use thereof as herbicidal agents
WO2022194843A1 (fr) 1,2,4-thiadiazoles substitués, leurs sels et leur utilisation comme substances actives herbicides
WO2022194842A1 (fr) 1,2,4-thiadiazoles substitués, leurs sels et leur utilisation comme substances actives herbicides
WO2022194841A1 (fr) 1,2,4-thiadiazoles substitués, leurs sels et leur utilisation comme substances actives herbicides
US20240352010A1 (en) Substituted 1,2,4-thiadiazolyl nicotinamides, salts or n-oxides thereof and their use as herbicidally active substances
WO2023165958A1 (fr) 1,2,4-thiadiazolyl isonicotinamides substitués, sels ou n-oxydes de ceux-ci et leur utilisation en tant que substances à action herbicide
WO2023165957A1 (fr) 1,2,4-thiadiazolyl picolinamides substitués, sels ou n-oxydes de ceux-ci et leur utilisation en tant que substances à action herbicide
WO2023020963A1 (fr) 1,2,4-thiadiazolyl nicotinamides substitués, leurs sels ou n-oxydes et leur utilisation comme substances actives herbicides
WO2023020962A1 (fr) 1,2,4-thiadiazolyl nicotinamides substitués, leurs sels ou n-oxydes et leur utilisation comme substances actives herbicides
AU2023246651A1 (en) Substituted 2-aminoazines and salts thereof, and use thereof as herbicidal active substances
CA3210359A1 (fr) (2-heteroaryloxyphenyl)sulfonates substitues, leurs sels et leur utilisation comme agents herbicides
WO2024194026A1 (fr) 4-difluorométhyl benzamides à action herbicide
CN118974024A (zh) 取代的2-c-吖嗪及其盐以及作为除草活性物质的用途
WO2023094594A1 (fr) Dihydropyranopyridines substituées, leurs sels ou n-oxydes et leur utilisation comme substances à action herbicide
CN118974025A (zh) 取代的2-氨基嗪及其盐，及其作为除草活性物质的用途
WO2022229055A1 (fr) Pyridazinones substituées, leurs sels ou n-oxydes et leur utilisation comme substances actives à action herbicide
WO2021028419A1 (fr) 3-(2-hétéroaryloxyphényle)isoxazolines substituées, leurs sels et leur utilisation en tant que substances actives herbicides
JP2024525526A (ja) 除草剤としてのｎ－（１，３，４－オキサジアゾール－２－イル）フェニルカルボキサミド
WO2021028421A1 (fr) (2-hétéroaryloxyphényle) isoxazolines substituées et leurs sels et leur utilisation en tant que substances actives herbicides
WO2020245097A1 (fr) Pyridinyloxypyridines substituées, leurs sels et leur utilisation comme agents herbicides
EP3747868A1 (fr) Phénoxypyridines substituées ainsi que leurs sels et leur utilisation en tant qu'agents herbicides
EP3747867A1 (fr) Pyridinyloxyanilines substituées ainsi que leurs sels et leur utilisation en tant qu'agents herbicides

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22714849

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22714849

Country of ref document: EP

Kind code of ref document: A1