WO2005000824A1 - Lazolidine derivatives as herbicidal agents - Google Patents

Lazolidine derivatives as herbicidal agents Download PDF

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Publication number
WO2005000824A1
WO2005000824A1 PCT/EP2004/006367 EP2004006367W WO2005000824A1 WO 2005000824 A1 WO2005000824 A1 WO 2005000824A1 EP 2004006367 W EP2004006367 W EP 2004006367W WO 2005000824 A1 WO2005000824 A1 WO 2005000824A1
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Prior art keywords
formula
hal
compounds
chc1
ocf
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PCT/EP2004/006367
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French (fr)
Inventor
Akihiko Yanagi
Yoshihiro Yamaguchi
Shinichi Narabu
Shinichi Shirakura
Shin Nakamura
Jun Mihara
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Bayer Cropscience Aktiengesellschaft
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Publication of WO2005000824A1 publication Critical patent/WO2005000824A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/24—Oxygen or sulfur atoms
    • C07D207/26—2-Pyrrolidones
    • C07D207/273—2-Pyrrolidones with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to other ring carbon atoms
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom 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
    • 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
    • A01N43/74—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 one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • 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
    • A01N43/74—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 one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/28—Nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/18—Nitrogen atoms

Definitions

  • the present invention relates to novel azolidinone derivatives, to processes for their preparation and to their use as herbicides.
  • R 1 represents halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, haloalkylthio or haloalkylene- dioxy
  • n 0, 1, 2, 3, 4 or 5
  • the R 1 substituents are identical or different, when m represents 2, 3, 4 or 5,
  • R 2 represents alkyl
  • X represents alkylidene, an oxygen atom or a sulfur atom
  • A represents one of the groups
  • Q-hal represents haloalkyl
  • Hal represents halogen
  • M represents halogen or a hydroxyl group
  • A has the same definition as aforementioned, in the presence of inert solvents, and if appropriate, in the presence of an acid binding agent or a condensing agent.
  • azolidine derivatives of the formula (I), according to the present invention show strong herbicidal activities. Though the azolidine derivatives of the formula (I) are included conceptually in the compounds of the general formula (I) described in WO 95/33719, they are novel compounds, which are not specifically described in said reference, and unexpectedly show an extremely strong herbicidal action, compared with known compounds of the prior art.
  • azolidine derivatives of the formula (I), according to the present invention can, therefore, be used as herbicides.
  • azolidine derivatives of the formula (I) can show even stronger herbicidal activity and better selectivity when being mixed with other herbicidally active compounds or safeners such as for instance those specifically mentioned below.
  • Halogen represents fluoro, chloro, bromo or iodo, preferably represents fluoro, chloro or bromo.
  • Alkyl can be straight-chain or branched-chain. There can be mentioned, for example, C ⁇ - 4 alkyl, and can be specifically mentioned methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, etc.
  • Alkoxy represents an Alkyl-O- group, whose alkyl part has the above-mentioned meaning. It represents, for example, - 4 . alkoxy, and specifically there can be mentioned methoxy, ethoxy, n- or iso-propoxy, n-, iso-, sec- or tert-butoxy, etc.
  • Haloalkyl represents straight-chain or branched-chain alkyl, in which at least one hydrogen is replaced by halogen, and there can be mentioned, for example, C 1 - 4 alkyl substituted with 1 to 6 fluoro, chloro and/or bromo atoms, and as specific examples there can be mentioned fluoromethyl, chloromethyl, dichloromethyl, bromomethyl, difluoromethyl, trifluoromethyl, chlorodifluoro- methyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-chloro-l,l,2-trifluoroethyl, 3- fluoropropyl, 3-chloropropyl, 2,2,3,3,3-pentafluoropropyl, 1,2,2,3,3,3-hexafluoropropyl, etc.
  • haloalkyl part in “haloalkoxy” and “haloalkylthio” can be of the same definition as in the aforementioned “haloalkyl” and there can be mentioned specifically as “haloalkoxy", for example, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, dichloromethoxy, 2-fluoroethoxy, 2- chloroethoxy, 2,2,2-trifluoroethoxy, 3-chloropropoxy, etc. and as "haloalkylthio" there can be mentioned, for example, difluoromethylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, 3-fluoro- propylthio, etc.
  • Haloalkylenedioxy can be straight-chain or branched-chain and there can be mentioned, for example, difluoromethylenedioxy, tetrafluoroethylenedioxy, l-methyl-2,2-difluoroethylene- dioxy, 1 , 1 -dimethyl-2,2-difluoroethylenedioxy, etc .
  • Alkylidene can be straight-chain or branched-chain and there can be mentioned, for example, methylene, ethylidene, n- or iso-propylidene, etc.
  • R 1 represents fluoro, chloro, bromo, C ⁇ - 4 alkyl, C ⁇ alkoxy, -.Jialoalkyl, - ⁇ aloalkoxy, .4. haloalkylthio or -.Jialoalkylenedioxy,
  • n 1, 2 or 3
  • R 2 represents methyl
  • X represents methylene, an oxygen atom or a sulfur atom
  • A represents one of the groups
  • Q-hal represents C ⁇ - 4 haloa_kyl
  • Hal represents chloro or bromo.
  • R 1 represents fluoro, chloro, bromo, methyl, methoxy, trifluoromethyl, chlorodifluoromethyl, trichloromethyl, difluoromethoxy, chlorodifluoromethoxy, trifluoromethoxy, trifluoro- ethoxy, dichloromethoxy, difluoromethylthio, trifluoromethylthio, difluoromethylenedioxy or tetrafluoroethylenedioxy,
  • n 1, 2 or 3
  • R 1 connects to the 3-position of the phenyl group, when m represents 1,
  • R 1 substituents connect to the 3-position and 4-position, or connect to the 3-position and 5- position of the phenyl group, and two R 1 substituents are identical or different, when m represents
  • R 1 substituents connect to the 3-position, 4-position and 5-position of the phenyl group, and three R 1 substituents are identical or different, when m represents 3,
  • R 2 represents methyl
  • X represents methylene, an oxygen atom or a sulfur atom
  • A represents one of the groups
  • Q represents methyl or tert-butyl
  • Q-hal represents fluoromethyl, chloromethyl, dichloromethyl or bromomethyl
  • Hal represents chloro or bromo.
  • the aforementioned preparation process (a) can be illustrated by the following reaction scheme in case that, for example, 5-N-methylamino- 3-(3-trifluoromethylphenyl)-4-thiazolidinone and 2,2- bis(chloromethyl)propanoyl chloride are used as the starting materials.
  • the compounds of the formula (II) used as the staring materials in the above mentioned preparation process (a) the following can be mentioned:
  • the compounds of the formula (Dl) used as starting materials in the above-mentioned preparation process (a) partly include novel compounds.
  • acid halides wherein M in the formula (T ⁇ ) represents halogen
  • M in the formula (T ⁇ ) represents halogen
  • a halogenating agent for example, phosphorus oxychloride, phosphorus oxybromide, phosphorus trichloride, phosphorus tribromide, phosgenes, oxalyl dichloride, thionyl chloride, thionyl bromide, etc.
  • Certain halogen-substituted acid halides are known compounds described in, for example, German Laid-open Patent Specification No. 3111848, German Laid-open Patent Specification No. 3326875, etc.
  • the carboxylic acids of the formula (HI), in which M represents a hydroxyl group include the 10 compounds well known in the field of organic chemistry and can be easily prepared by such processes as hydrolysis of esters, oxidation of alcohols, aldehydes or ketones, etc.
  • the reaction of the above-mentioned preparation process (a) can be conducted in an appropriate diluent.
  • diluent used in that case there can be mentioned, for example, aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclo-
  • ethers for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetra- hydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc.; ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone (MIBK), etc.;
  • nitriles for example, acetonitrile, propionitrile, etc.
  • esters for example, ethyl acetate, amyl acetate, etc.
  • acid amides for example, dimethylformamide (DMF), dimethylacetamide (DMA), N- methylpyrrolidone, etc.
  • sulfones and sulfoxides for example, dimethyl sulfoxide (DMSO), sulfolane, etc.
  • bases for example, pyridine etc.
  • the preparation process (a) can be conducted in the presence of an acid binding agent or 25. condensing agent.
  • an acid binding agent or 25. condensing agent As the usable acid binder there can be mentioned, as inorganic base, hydrides, carbonates etc. of alkali metals, for example, sodium hydride, lithium hydride, sodium carbonate, potassium carbonate, etc.; and as organic base, tertiary amines, dialkylaminoanilines, and pyridines, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), pyridine, 4- dimethylaminopyridine (DMAP), l,4-diazabicyclo[2,2,2]octane (DABCO), 1,8-diazabicyclo- 30 [5,4,0]undec-7-ene (DBU), etc., and as condensing agent there can be mentioned carbodiimides; for example, N,N'-dicyclohe
  • the preparation process (a) can be conducted in a substantially wide range of temperature. However, the temperatures in the range of eenerally about -20 to about 140°C, preferably about 0 to about 100°C are adequate. Although said reaction is conducted desirably under normal pressure, it can be operated optionally under elevated pressure or under reduced pressure.
  • said preparation process can be conducted optionally by adding an additive, in case that M in the formula (HI) represents a hydroxyl group, and as the usable additive there can be mentioned, for example, N-hydroxybenzotriazole, N-hydroxysucciniinide, 3,4-dihydro-3-hydroxy-4-oxo- 1,2,3-benzotriazine, etc.
  • the compounds of the formula (I) can be obtained, for example, by reacting 1 to 5 moles of a compound of the formula (ID) to 1 mole of a compound of the formula (II) in a diluent, for example, tetrahydrofuran, in the presence of 1 to 5 moles of triethylamine.
  • a diluent for example, tetrahydrofuran
  • the active compounds of the aforementioned formula (I) according to the present invention show, as shown in the biological test examples described below, excellent herbicidal activities against various weeds and can be used as herbicides.
  • weeds mean, in a broader sense, all plants that grow in locations where they are not desired.
  • the compounds of the present invention act as total or selective herbicide depending upon the applied concentration.
  • the active compounds of the present invention can be used, for example, between the following weeds and cultures.
  • the active compounds of the formula (I) according to the present invention can, as aforementioned, show even stronger herbicidal effect and selectivity when being mixed with other herbicidally active compounds or safeners.
  • Genera of the dicotyledonous weeds Sinapis, Leipidium, Galium, Stellaria, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Ipomoea, Polygonum, Ambrosia, Cirsium, Sonchus, Solanum, Rorippa, Lamium, Veronica, Datura, Viola, Galeopsis, Papaver, Centaurea, Galinsoga, Rotala, Lindernia, etc.
  • Genera of the dicotyledonous cultures Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita, etc.
  • Genera of the monocotyledonous weeds Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Agrostis, Alopecurus, Cynodon, etc.
  • Genera of the monocotyledonous cultures Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium, etc.
  • the active compounds of the formula (I) according to the present invention, and mixed herbicidal compositions can be used particularly against paddy field weeds.
  • paddy field weeds that can be controlled by using the compounds of the formula (I)
  • mixed herbicidal compositions there can be specifically mentioned, for example, Rotala indica Koehne, Lindernia Procumbens Philcox, Ludwigia prostrata Roxburgh, Potamogeton distinctus A.
  • the active compounds of the formula (I) according to the present invention, and mixed herbicidal compositions can be used against weeds that show resistance against sulfonylurea type herbicides.
  • the active compounds of the present invention can, depending upon the applied concentration, non-selectively control weeds and can be used, for example, on industrial terrain such as factories, rail tracks, paths, places with or without tree plantings.
  • the active compounds of the present invention can be used for controlling weeds in perennial cultures and can be applied, for example, in afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings, hop fields, etc. Further, they can be applied for the selective weed control in annual cultures.
  • the active compounds according to the present invention, and mixed herbicidal compositions can be converted into customary formulation forms on actual application.
  • formulation forms there can be mentioned, for example, solutions, wettable powders, emulsions, suspensions, powders, water dispersible granules, tablets, granules, suspo-emulsion concentrates, microcapsules in polymer substance, jumbo formulations, etc.
  • formulations can be prepared according to per se known methods, for example, by mixing the active compounds with extenders, namely liquid or solid diluents or carriers, and optionally with surface-active agents, namely emulsifiers and/or dispersants and/or foam-forming agents.
  • extenders namely liquid or solid diluents or carriers
  • surface-active agents namely emulsifiers and/or dispersants and/or foam-forming agents.
  • liquid diluents or carriers there can be mentioned, for example, aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic hydrocarbons [for example, cyclohexane etc.
  • aromatic hydrocarbons for example, xylene, toluene, alkylnaphthalene, etc.
  • chlorinated aromatic or chlorinated aliphatic hydrocarbons for example, chlorobenzenes, ethylene chlorides, methylene chloride, etc.
  • aliphatic hydrocarbons for example, cyclohexane etc.
  • paraffins for example, mineral oil fractions etc.
  • alcohols for example, butanol, glycols, etc.
  • ethers for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
  • strongly polar solvents for example, dimethylformamide, dimethyl sulfoxide, etc.
  • nonionic and anionic emulsifiers for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (for example, alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, aryl- sulfonates, etc.)], albumin hydrolysis products, etc.
  • Dispersants include, for example, lignin sulfite waste liquor, methyl cellulose, etc.
  • Tackifiers can also be used in formulations (powders, granules, emulsifiable concentrates).
  • tackifiers there can be mentioned, for example, carboxymethyl cellulose, natural and synthetic polymers (for example, gum Arabic, polyvinyl alcohol, polyvinyl acetate, etc.).
  • Colorants can also be used.
  • inorganic pigments for example, iron oxide, titanium oxide, Prussian Blue, etc,
  • organic dyestuffs such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs
  • nutrients such as salts of metals such as iron, manganese, boron, copper, cobalt, molybdenum, zinc, etc.
  • Said formulations can contain the active compounds of the formula (I) in the range of generally 0.1 to 95 % by weight, preferably 0.5 to 90 % by weight.
  • the active compounds of the formula (I) according to the present invention can be used for weed control as themselves or in their formulation forms.
  • the mixed herbicidal compositions with known herbicides can be previously prepared in the final formulation forms or can be prepared by tank mixing when they are used.
  • the herbicides that can be used as mixed herbicidal compositions in combination with the compounds of the formula (I) there can be mentioned, for example, the following herbicides represented by generic names as specific examples:
  • acetamide type herbicides for example, pretilachlor, butachlor, thenylchlor, alachlor, etc.; amide type herbicides: for example, clomeprop, etobenzanid, etc.; benzofuran type herbicides: for example, benfuresate etc.; indandione type herbicides: for example, indanofan etc.; pyrazole type herbicides: for example, pyrazolate, benzofenap, pyrazoxifen, etc.; oxazinone type herbicides: for example, oxaziclomefone etc.; sulfonylurea type herbicides: for example, bensulfuron-methyl, azimsulfuron, imazosulfuron, pyrazosulfuron-ethyl, cyclosulfamuron, ethoxysulfuron, halosulfuron-methyl, etc.; thiocarbamate type herbicides: for example
  • the active compounds of the formula (I) can be directly used as such or used in formulation forms such as ready-to-use solutions, emulsifiable concentrates, tablets, suspensions, powders, pastes or granules, or used in use forms prepared by further dilution.
  • the active compounds of the present invention can be applied by means of, for example, watering, spraying, atomizing, granule application, etc.
  • the active compounds of the formula (I) can be used at any stages before and after germination of plants. They can be also mixed into the soil before sowing.
  • the application amount of the active compounds of the formula (I) can be varied in a substantial range. It is fundamentally different depending upon the properties of effects to be desired. In case of using as herbicide, there can be mentioned application rates in the range of, for example, about 0.01 to about 4 kg, preferably about 0.05 to about 3 kg as active compound per hectare.
  • plants and their parts are treated.
  • wild plant species and plant cultivars or those obtained by conventional biological breeding, such as crossing or protoplast fusion, and parts thereof, are treated.
  • transgenic plants and plant cultivars obtained by genetic engineering if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated.
  • the term "parts” or “parts of plants” or “plant parts” has been explained above.
  • plants of the plant cultivars which are in each case commercially available or in use are treated according to the invention.
  • Plant cultivars are to be understood as meaning plants having certain properties ("traits") and which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be cultivars, bio- or genotypes.
  • the treatment according to the invention may also result in superadditive ("synergistic") effects.
  • superadditive for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the substances and compositions which can be used according to the invention - also in combination with other agro- chemical active compounds -, better plant growth, increased tolerance of the crop plants to high or low temperatures, increased tolerance of the crop plants to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products are possible which exceed the effects which were actually to be expected.
  • the preferred transgenic plants or plant cultivars which are to be treated according to the invention include all plants which, in the genetic modification, received genetic material which imparted particularly advantageous useful properties ("traits") to these plants.
  • traits particularly advantageous useful properties
  • Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products.
  • transgenic plants which may. be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soya beans, potatoes, cotton, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), and particular emphasis is given to maize, soya beans, potatoes, cotton and oilseed rape.
  • Traits that are emphasized in particular are increased defence of the plants against insects by toxins formed in the plants, in particular those formed in the plants by the genetic material from
  • Bacillus thuringiensis (for example by the genes Cry ⁇ A(a), CryIA(b), Cry ⁇ A(c), CryDA, CrylDA,
  • Bt plants CryDIB2, Cry9c, Cry2Ab, Cry3Bb and CrylF and also combinations thereof
  • Bt plants Traits that are also particularly emphasized are the increased defence of the plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins.
  • SAR systemic acquired resistance
  • Traits that are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinothricin (for example the "PAT" gene).
  • genes which impart the desired traits in each case can also be present in combinations with one another in the transgenic plants.
  • "Bt plants” which may be mentioned are maize varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade names YIELD GARD® (for example maize, cotton, soya beans), KnockOut® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato).
  • herbicide-tolerant plants examples include maize varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soya bean), Liberty Link® (tolerance to phosphinothricin, for example oilseed rape), Evil® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example maize).
  • Herbicide-resistant plants plants bred in a conventional manner for herbicide tolerance
  • Clearfield® for example maize
  • the plants listed can be treated according to the invention in a particularly advantageous manner with the compounds of the general formula (I) or the active compound mixtures according to the invention, where in addition to the good control of weed plants, the above-mentioned synergistic effects with the transgenic plants or plant cultivars occur.
  • the preferred ranges stated above for the active compounds or mixtures also apply to the treatment of these plants. Particular emphasis is given to the treatment of plants with the compounds or mixtures specifically mentioned in the present text.
  • 2,2-Bis(chloromethyl)propanoyl chloride (0.34g) was dissolved in THF (5ml) and added dropwise to a solution of 5-N-methylamino- 3-(3-trifluoromethylphenyl)-4-thiazolidinone (0.50 g) and tri- ethylamine (0.18g) in THF (10ml) at room temperature and the mixed solution was stirred for 3 hours. After the reaction, cold water was added to the reaction mixture, and the reaction mixture was extracted with ethyl acetate (50ml), washed with a saturated aqueous solution of sodium chloride, and dried over anhydrous magnesium sulfate.
  • Me represents methyl and t-Bu represents tert-butyl.
  • Test Example 1 Test for herbicidal activity against paddy field weeds
  • DMF Dimethylformamide
  • Emulsifier Benzyloxy polyglycol ether 1 part by weight
  • a formulation of an active substance is obtained as an emulsifiable concentrate by mixing 1 part by weight of the active compound with the above-mentioned amount of the carrier and emulsifier. A prescribed amount of the formulation is diluted with water.
  • the rate of herbicidal activity was examined 4 weeks after the treatment.
  • the compounds of examples No. 168, 171, 176, 261 and 281 showed herbicidal activity of higher than 90% against Echinochloa crusgalli, Setaria viridis, Amaranthus retroflexus and Polygonum at the application rate (amount of the active component) of 0.06kg/ha.
  • Test Example 3 Test of post-emergence foliage treatment against field weeds
  • Clay mineral particles (95 parts) having particle diameter distribution in the range of 0.2 to 2mm are put in a rotary mixer. While rotating it, the compound of the present invention No.49 (5 parts) is sprayed together with a liquid diluent, wetted uniformly and dried at 40 to 50°C to obtain granules.
  • the compound of the present invention No. 261 (30 parts), xylene (5 parts), polyoxyethylene alkyl phenyl ether (8 parts) and calcium alkylbenzenesulfonate (7 parts) are mixed and stirred to obtain an emulsifiable concentrate.
  • the compound of the present invention No. 281 (15 Parts), a mixture of white carbon (hydrous amorphous silicon oxide fine powders) and powder clay (1:5) (80 parts), sodium alkylbenzenesulfonate (2 parts) and sodium alkylnaphthalenesulfonate-formalin-condensate (3 parts) are crushed and mixed to make a wettable powder.
  • the compound of the present invention No. 176 (20 Parts), sodium ligmnsulfonate (30 parts), bentonite (15 parts) and calcined diatomaceous earth (35 parts) are well mixed, added with water, extruded with 0.3mm screen and dried to obtain water dispersible granules.

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Abstract

Novel azolidine derivatives of the formula (I) wherein R1 represents halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, haloalkylthio or haloalkylene-dioxy, m represents 0, 1, 2, 3, 4 or 5, the R1 substituents are identical or different each other, when m represents 2, 3, 4 or 5, R2 represents alkyl, X represents alkylidene, oxygen atom or sulfur atom, and A represents one of the groups described in the specification and their use as herbicides.

Description

AZOLIDINE DERIVATIVES AS HΞRBICIDAL AGENTS
The present invention relates to novel azolidinone derivatives, to processes for their preparation and to their use as herbicides.
It has been already known that certain azolidine derivatives show an action as herbicide (cf . WO 95/33719, WO 97/20838, WO 00/21928 and American Chemical Society, 18-29 (2002)).
The known derivatives disclosed in the above-mentioned publications, however, are not satisfactory enough in terms of effects and/or selectivity as herbicide.
There have now been found novel azolidine derivatives of the formula (I)
Figure imgf000002_0001
wherein
R1 represents halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, haloalkylthio or haloalkylene- dioxy,
m represents 0, 1, 2, 3, 4 or 5, the R1 substituents are identical or different, when m represents 2, 3, 4 or 5,
R2 represents alkyl,
X represents alkylidene, an oxygen atom or a sulfur atom, and
A represents one of the groups
Figure imgf000002_0002
Figure imgf000003_0001
Figure imgf000003_0002
Figure imgf000003_0003
or
-C — Hal (A-5), H
wherein
Q represents alkyl,
Q-hal represents haloalkyl, and
Hal represents halogen.
The compounds of the formula (I), according to the invention, can be obtained by a process in which
a) compounds of the formula (IT)
Figure imgf000003_0004
wherein R1, m, R2 and X have the same definition as aforementioned, are reacted with compounds of the formula(IH)
Figure imgf000004_0001
wherein M represents halogen or a hydroxyl group, and
A has the same definition as aforementioned, in the presence of inert solvents, and if appropriate, in the presence of an acid binding agent or a condensing agent.
The azolidine derivatives of the formula (I), according to the present invention show strong herbicidal activities. Though the azolidine derivatives of the formula (I) are included conceptually in the compounds of the general formula (I) described in WO 95/33719, they are novel compounds, which are not specifically described in said reference, and unexpectedly show an extremely strong herbicidal action, compared with known compounds of the prior art.
The azolidine derivatives of the formula (I), according to the present invention can, therefore, be used as herbicides.
The azolidine derivatives of the formula (I) can show even stronger herbicidal activity and better selectivity when being mixed with other herbicidally active compounds or safeners such as for instance those specifically mentioned below.
In the present specification
"Halogen" represents fluoro, chloro, bromo or iodo, preferably represents fluoro, chloro or bromo.
"Alkyl" can be straight-chain or branched-chain. There can be mentioned, for example, Cι-4 alkyl, and can be specifically mentioned methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, etc.
"Alkoxy" represents an Alkyl-O- group, whose alkyl part has the above-mentioned meaning. It represents, for example, -4. alkoxy, and specifically there can be mentioned methoxy, ethoxy, n- or iso-propoxy, n-, iso-, sec- or tert-butoxy, etc. "Haloalkyl" represents straight-chain or branched-chain alkyl, in which at least one hydrogen is replaced by halogen, and there can be mentioned, for example, C1-4 alkyl substituted with 1 to 6 fluoro, chloro and/or bromo atoms, and as specific examples there can be mentioned fluoromethyl, chloromethyl, dichloromethyl, bromomethyl, difluoromethyl, trifluoromethyl, chlorodifluoro- methyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-chloro-l,l,2-trifluoroethyl, 3- fluoropropyl, 3-chloropropyl, 2,2,3,3,3-pentafluoropropyl, 1,2,2,3,3,3-hexafluoropropyl, etc.
The haloalkyl part in "haloalkoxy" and "haloalkylthio" can be of the same definition as in the aforementioned "haloalkyl" and there can be mentioned specifically as "haloalkoxy", for example, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, dichloromethoxy, 2-fluoroethoxy, 2- chloroethoxy, 2,2,2-trifluoroethoxy, 3-chloropropoxy, etc. and as "haloalkylthio" there can be mentioned, for example, difluoromethylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, 3-fluoro- propylthio, etc.
"Haloalkylenedioxy" can be straight-chain or branched-chain and there can be mentioned, for example, difluoromethylenedioxy, tetrafluoroethylenedioxy, l-methyl-2,2-difluoroethylene- dioxy, 1 , 1 -dimethyl-2,2-difluoroethylenedioxy, etc .
"Alkylidene" can be straight-chain or branched-chain and there can be mentioned, for example, methylene, ethylidene, n- or iso-propylidene, etc.
As a preferable group of compounds of the present invention there can be mentioned the compounds of the aforementioned formula (I) wherein
R1 represents fluoro, chloro, bromo, Cι-4alkyl, C^alkoxy, -.Jialoalkyl, -^aloalkoxy, .4. haloalkylthio or -.Jialoalkylenedioxy,
m represents 1, 2 or 3,
R2 represents methyl,
X represents methylene, an oxygen atom or a sulfur atom, and
A represents one of the groups
Figure imgf000006_0001
Figure imgf000006_0002
Figure imgf000006_0003
or Q -C- Hal (A-5), H
wherein
Q represents Cι_4alkyl,
Q-hal represents Cι-4haloa_kyl, and
Hal represents chloro or bromo.
As a more preferable group of compounds of the present invention there can be mentioned the compounds of the aforementioned formula (I) wherein
R1 represents fluoro, chloro, bromo, methyl, methoxy, trifluoromethyl, chlorodifluoromethyl, trichloromethyl, difluoromethoxy, chlorodifluoromethoxy, trifluoromethoxy, trifluoro- ethoxy, dichloromethoxy, difluoromethylthio, trifluoromethylthio, difluoromethylenedioxy or tetrafluoroethylenedioxy,
m represents 1, 2 or 3,
R1 connects to the 3-position of the phenyl group, when m represents 1,
two R1 substituents connect to the 3-position and 4-position, or connect to the 3-position and 5- position of the phenyl group, and two R1 substituents are identical or different, when m represents
2,
three R1 substituents connect to the 3-position, 4-position and 5-position of the phenyl group, and three R1 substituents are identical or different, when m represents 3,
R2 represents methyl,
X represents methylene, an oxygen atom or a sulfur atom, and
A represents one of the groups
Figure imgf000007_0001
Figure imgf000007_0002
Figure imgf000007_0003
Figure imgf000008_0001
or Q C— Hal (A-5), H
wherein
Q represents methyl or tert-butyl,
Q-hal represents fluoromethyl, chloromethyl, dichloromethyl or bromomethyl, and
Hal represents chloro or bromo.
The aforementioned preparation process (a) can be illustrated by the following reaction scheme in case that, for example, 5-N-methylamino- 3-(3-trifluoromethylphenyl)-4-thiazolidinone and 2,2- bis(chloromethyl)propanoyl chloride are used as the starting materials.
Figure imgf000008_0002
The compounds of the formula (II) used as the starting materials in the aforementioned preparation process (a), a part of which are novel compounds that were not described yet in the literature, can be easily prepared by the process described in, for example, WO 00/21928 , WO 95/33719, etc. As typical examples of the compounds of the formula (II) used as the staring materials in the above mentioned preparation process (a), the following can be mentioned:
5-N-methylamino- 3-(3-trifluoromethylphenyl)-4-thiazolidinone, 5-N-methylamino- 3-(3-trifluoromethoxyphenyl)-4-thiazolidinone, 5-N-methylamino- 3-(3-chloro-4-fluorophenyl)-4-thiazolidinone, 5-N-methylamino- 3-(3-bromo-4-fluorophenyl)-4-thiazolidinone, 5-N-methylamino- 3-(4-fluoro-3-trifluoromethylphenyl)-4-thiazolidinone, 5-N-methylamino- 3-(4-chloro-3-trifluoromethylphenyl)-4-thiazolidinone, 5-N-methylamino- 3-(3-trifluoromethylthiophenyl)-4-thiazolidinone, 3-N-methylamino- l-(3-trifluoromethylphenyl)-2-pyrrolidinone, 3-N-methylamino- l-[3,4-bis(trifluoromethyl)phenyl]-2-pyrrolidinone, 3-N-methylamino- 1 -(3-trifluoromethoxyphenyl)-2-pyrrolidinone, 3-N-methylamino- l-(3-difluoromethoxyphenyl)-2-pyrrolidinone, 3-N-methylamino- 1 -(3-chloro-4-fluoroρhenyl)-2-pyrrolidinone, 3-N-methylamino- 1 -(4-chloro-3-trifluoromethylphenyl)-2-pyrrolidinone, 3-N-methylamino- l-(3-methoxy-4-methylphenyl)-2-pyrrolidinone, 5-N-methylamino- 3-(3-trifluoromethylphenyl)-4-oxazolidinone, 5-N-methylamino- 3-(3-trifluoromethoxyphenyl)-4-oxazolidinone, 5-N-methylamino- 3-(3-difluoromethoxyphenyl)-4-oxazolidinone, 5-N-methylamino- 3-(3-chloro-4-fluorophenyl)-4-oxazolidinone, 5-N-methylamino- 3-(3,5-dichloro-4-fluorophenyl)-4-oxazolidinone, 5-N-methylamino- •3-(4-chloro-3-trifluoromethylρhenyl)-4-oxazolidinone, and so on.
The compounds of the formula (Dl) used as starting materials in the above-mentioned preparation process (a) partly include novel compounds. For example, acid halides, wherein M in the formula (TΩ) represents halogen, can be prepared by reacting the corresponding carboxylic acids, wherein M respectively represents a hydroxyl group, with a halogenating agent, for example, phosphorus oxychloride, phosphorus oxybromide, phosphorus trichloride, phosphorus tribromide, phosgenes, oxalyl dichloride, thionyl chloride, thionyl bromide, etc. Certain halogen-substituted acid halides are known compounds described in, for example, German Laid-open Patent Specification No. 3111848, German Laid-open Patent Specification No. 3326875, etc.
As typical examples of the compounds of the formula (W), used as the starting materials in the above- mentioned preparation process (a) the following can be mentioned:
3-chloro-2,2-dimethylpropanoyl chloride, 2,2-bis(chloromethyl)propanoyl chloride, 3,3-dichloro-2,2-dimethylpropanoyl chloride, 3-fluoro-2,2-dimethylpropanoyl chloride, 2,2-bis(fluoromethyl)propanoyl chloride, 3-chloro-2,2-dimethylpropionic acid, 5 2,2-bis(chloromethyl)propionic acid, 3,3-dichloro-2,2-dimethylpropionic acid, 3-fluoro-2,2-dimethylproρionic acid, 2,2-bis(fluoromethyl)propionic acid, and so on.
The carboxylic acids of the formula (HI), in which M represents a hydroxyl group, include the 10 compounds well known in the field of organic chemistry and can be easily prepared by such processes as hydrolysis of esters, oxidation of alcohols, aldehydes or ketones, etc.
The reaction of the above-mentioned preparation process (a) can be conducted in an appropriate diluent. As the diluent used in that case there can be mentioned, for example, aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclo-
15 hexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetra- hydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc.; ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone (MIBK), etc.;
20 nitriles, for example, acetonitrile, propionitrile, etc.; esters, for example, ethyl acetate, amyl acetate, etc.; acid amides, for example, dimethylformamide (DMF), dimethylacetamide (DMA), N- methylpyrrolidone, etc.; sulfones and sulfoxides, for example, dimethyl sulfoxide (DMSO), sulfolane, etc.; bases, for example, pyridine etc.
The preparation process (a) can be conducted in the presence of an acid binding agent or 25. condensing agent. As the usable acid binder there can be mentioned, as inorganic base, hydrides, carbonates etc. of alkali metals, for example, sodium hydride, lithium hydride, sodium carbonate, potassium carbonate, etc.; and as organic base, tertiary amines, dialkylaminoanilines, and pyridines, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), pyridine, 4- dimethylaminopyridine (DMAP), l,4-diazabicyclo[2,2,2]octane (DABCO), 1,8-diazabicyclo- 30 [5,4,0]undec-7-ene (DBU), etc., and as condensing agent there can be mentioned carbodiimides; for example, N,N'-dicyclohexylcarbodiimide, N-(3-dimethylaminopropyl)- N'-ethylcarbodiimide hydrochloride, etc.
The preparation process (a) can be conducted in a substantially wide range of temperature. However, the temperatures in the range of eenerally about -20 to about 140°C, preferably about 0 to about 100°C are adequate. Although said reaction is conducted desirably under normal pressure, it can be operated optionally under elevated pressure or under reduced pressure.
Further, said preparation process can be conducted optionally by adding an additive, in case that M in the formula (HI) represents a hydroxyl group, and as the usable additive there can be mentioned, for example, N-hydroxybenzotriazole, N-hydroxysucciniinide, 3,4-dihydro-3-hydroxy-4-oxo- 1,2,3-benzotriazine, etc.
In conducting the preparation process (a), the compounds of the formula (I) can be obtained, for example, by reacting 1 to 5 moles of a compound of the formula (ID) to 1 mole of a compound of the formula (II) in a diluent, for example, tetrahydrofuran, in the presence of 1 to 5 moles of triethylamine.
The active compounds of the aforementioned formula (I) according to the present invention, show, as shown in the biological test examples described below, excellent herbicidal activities against various weeds and can be used as herbicides. In the present specification "weeds" mean, in a broader sense, all plants that grow in locations where they are not desired. The compounds of the present invention act as total or selective herbicide depending upon the applied concentration. The active compounds of the present invention can be used, for example, between the following weeds and cultures.
Moreover, the active compounds of the formula (I) according to the present invention, can, as aforementioned, show even stronger herbicidal effect and selectivity when being mixed with other herbicidally active compounds or safeners.
Genera of the dicotyledonous weeds: Sinapis, Leipidium, Galium, Stellaria, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Ipomoea, Polygonum, Ambrosia, Cirsium, Sonchus, Solanum, Rorippa, Lamium, Veronica, Datura, Viola, Galeopsis, Papaver, Centaurea, Galinsoga, Rotala, Lindernia, etc.
Genera of the dicotyledonous cultures: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita, etc.
Genera of the monocotyledonous weeds: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Agrostis, Alopecurus, Cynodon, etc. Genera of the monocotyledonous cultures: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium, etc.
The active compounds of the formula (I) according to the present invention, and mixed herbicidal compositions can be used particularly against paddy field weeds. As paddy field weeds that can be controlled by using the compounds of the formula (I), and mixed herbicidal compositions there can be specifically mentioned, for example, Rotala indica Koehne, Lindernia Procumbens Philcox, Ludwigia prostrata Roxburgh, Potamogeton distinctus A. Benn, Elatine triandra Schk, Oenanthe javanica, Echinochloa oryzicola Vasing, Monochoria vaginalis Presl, Eleocharis acicularis L., Eleocharis Kuroguwai Okwi, Cyperus difformis L., Cyperus serotinus Rottboel, Sagittaria pygmaea Miq, Alisma canaliculatum A. Br. Et Bouche, Scirpus juncoides Roxburgh etc. Moreover, the active compounds of the formula (I) according to the present invention, and mixed herbicidal compositions can be used against weeds that show resistance against sulfonylurea type herbicides.
As said resistant weeds there can be specifically mentioned, for example, Rotala indica Koehne, Lindernia Procumbens Philcox, Lindernia dubia L. PENNEL, Lindernia var. dubia Pennell, Lindernia angustifolia Wettstein, Elatine triandra Schk, Monochoria korsakowii REGEL & MAACK, Monochoria vaginalis Presl, Scirpus juncoides Roxburgh etc. The use of the active compounds of the formula (I) and mixed herbicidal compositions, however, is not restricted to the use against these weeds but can be applied against other paddy field weeds and other weeds than the sulfonylurea type herbicide-resistant weeds in a similar manner.
The use of the compounds of the formula (I), is not restricted to the above-mentioned plants, but can be applied against other plants in a similar manner.
The active compounds of the present invention can, depending upon the applied concentration, non-selectively control weeds and can be used, for example, on industrial terrain such as factories, rail tracks, paths, places with or without tree plantings. Moreover, the active compounds of the present invention can be used for controlling weeds in perennial cultures and can be applied, for example, in afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings, hop fields, etc. Further, they can be applied for the selective weed control in annual cultures.
The active compounds according to the present invention, and mixed herbicidal compositions can be converted into customary formulation forms on actual application. As such formulation forms there can be mentioned, for example, solutions, wettable powders, emulsions, suspensions, powders, water dispersible granules, tablets, granules, suspo-emulsion concentrates, microcapsules in polymer substance, jumbo formulations, etc.
These formulations can be prepared according to per se known methods, for example, by mixing the active compounds with extenders, namely liquid or solid diluents or carriers, and optionally with surface-active agents, namely emulsifiers and/or dispersants and/or foam-forming agents.
As liquid diluents or carriers there can be mentioned, for example, aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic hydrocarbons [for example, cyclohexane etc. or paraffins (for example, mineral oil fractions etc.)], alcohols (for example, butanol, glycols, etc.) and their ethers, esters, etc., ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), strongly polar solvents (for example, dimethylformamide, dimethyl sulfoxide, etc.), water, etc
As emulsifiers and/or foam-forming agents there can be mentioned, for example, nonionic and anionic emulsifiers [for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (for example, alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, aryl- sulfonates, etc.)], albumin hydrolysis products, etc.
Dispersants include, for example, lignin sulfite waste liquor, methyl cellulose, etc.
Tackifiers can also be used in formulations (powders, granules, emulsifiable concentrates). As said tackifiers there can be mentioned, for example, carboxymethyl cellulose, natural and synthetic polymers (for example, gum Arabic, polyvinyl alcohol, polyvinyl acetate, etc.).
Colorants can also be used. As said colorants there can be mentioned inorganic pigments (for example, iron oxide, titanium oxide, Prussian Blue, etc,), organic dyestuffs such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and further traces nutrients such as salts of metals such as iron, manganese, boron, copper, cobalt, molybdenum, zinc, etc.
Said formulations can contain the active compounds of the formula (I) in the range of generally 0.1 to 95 % by weight, preferably 0.5 to 90 % by weight.
The active compounds of the formula (I) according to the present invention, can be used for weed control as themselves or in their formulation forms. And the mixed herbicidal compositions with known herbicides can be previously prepared in the final formulation forms or can be prepared by tank mixing when they are used. As the herbicides that can be used as mixed herbicidal compositions in combination with the compounds of the formula (I) there can be mentioned, for example, the following herbicides represented by generic names as specific examples:
acetamide type herbicides: for example, pretilachlor, butachlor, thenylchlor, alachlor, etc.; amide type herbicides: for example, clomeprop, etobenzanid, etc.; benzofuran type herbicides: for example, benfuresate etc.; indandione type herbicides: for example, indanofan etc.; pyrazole type herbicides: for example, pyrazolate, benzofenap, pyrazoxifen, etc.; oxazinone type herbicides: for example, oxaziclomefone etc.; sulfonylurea type herbicides: for example, bensulfuron-methyl, azimsulfuron, imazosulfuron, pyrazosulfuron-ethyl, cyclosulfamuron, ethoxysulfuron, halosulfuron-methyl, etc.; thiocarbamate type herbicides: for example, thiobencarb, molinate, pyributycarb, etc.; triazine type herbicides: for example, dimethametryn, simetryn, etc.; triazole type herbicides: for example, cafenstrole etc.; quinoline type herbicides: for example, quinclorac etc.; isoxazole type herbicides: for example, isoxaflutole etc.; dithiophosphate type herbicides: for example, anilofos etc.; oxyacetamide type herbicides: for example, mefenacet, flufenacet, etc.; tetrazolinone type herbicides: for example, fentrazamide etc.; dicarboxyimide type herbicides: for example, pentoxazone etc.; trione type herbicides: for example, sulcotrione, benzobicyclon, etc.; phenoxypropinate type herbicides: for example, cyhalofop-butyl etc.; benzoic acid type herbicides: for example, pyrimenobac-methyl etc.; diphenyl ether type herbicides: for example, chlomethoxyfen, oxyfluorfen, etc.; pyridine dicarbothioate type herbicides: for example, dithiopyr etc.; phenoxy type herbicides: for example, MCPA, MCPB, etc.; urea type herbicides: for example, dymron, cumyluron, etc.; naphthalenedione type herbicides: for example, quinoclamine etc.; isoxazolidinone type herbicides: for example, clomazone etc.
The above-mentioned active compounds are known herbicides described in for instance in the "Pesticide Manual" published in 2000 by British Crop Protection Council.
Further, when the active compounds of the formula (I) are mixed with safeners, phytotoxicity is reduced by the mixing and a broader weed controlling spectrum is provided and the application as a selective herbicide can be broadened. As said safeners there can be mentioned, for example, the following compounds represented by generic names or development codes:
AD-67, BAS-145138, benoxacor, cloquintocet-mexyl, cyometrinil, 2,4-D, DKA-24, dichlormid, dymron, fenclorim, fenchlorazole-ethyl, flurazole, fluxofenim, isoxadifen-ethyl, mefenpyr-diethyl, MG-191, naphthalic anhydride, oxabetrinil, PPG-1292, R-29148, etc.
The above-mentioned safeners are also described in the "Pesticide Manual" published in 2000 by British Crop Protect Council.
Moreover, it is possible to further mix the above-mentioned safeners to a mixed herbicide composition consisting of the compounds of the formula (I) and an above-mentioned herbicide. By the mixing phytotoxicity is reduced and a broader weed controlling spectrum is provided and the application as a selective herbicide can be broadened.
Surprisingly, some of the mixed herbicide compositions consisting of a compound of the present invention and a known herbicide and/or a safener can show synergistic effects.
In case of using the active compounds of the formula (I) they can be directly used as such or used in formulation forms such as ready-to-use solutions, emulsifiable concentrates, tablets, suspensions, powders, pastes or granules, or used in use forms prepared by further dilution. The active compounds of the present invention can be applied by means of, for example, watering, spraying, atomizing, granule application, etc.
The active compounds of the formula (I) can be used at any stages before and after germination of plants. They can be also mixed into the soil before sowing.
The application amount of the active compounds of the formula (I) can be varied in a substantial range. It is fundamentally different depending upon the properties of effects to be desired. In case of using as herbicide, there can be mentioned application rates in the range of, for example, about 0.01 to about 4 kg, preferably about 0.05 to about 3 kg as active compound per hectare.
It is possible to treat all plants and their parts according to the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding, such as crossing or protoplast fusion, and parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated. The term "parts" or "parts of plants" or "plant parts" has been explained above. Particularly preferably, plants of the plant cultivars which are in each case commercially available or in use are treated according to the invention. Plant cultivars are to be understood as meaning plants having certain properties ("traits") and which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be cultivars, bio- or genotypes.
Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive ("synergistic") effects. Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the substances and compositions which can be used according to the invention - also in combination with other agro- chemical active compounds -, better plant growth, increased tolerance of the crop plants to high or low temperatures, increased tolerance of the crop plants to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products are possible which exceed the effects which were actually to be expected.
The preferred transgenic plants or plant cultivars (i.e. those obtained by genetic engineering) which are to be treated according to the invention include all plants which, in the genetic modification, received genetic material which imparted particularly advantageous useful properties ("traits") to these plants. Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products. Further and particularly emphasized examples of such properties are a better defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance of the plants to certain herbicidally active compounds. Examples of transgenic plants which may. be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soya beans, potatoes, cotton, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), and particular emphasis is given to maize, soya beans, potatoes, cotton and oilseed rape. Traits that are emphasized in particular are increased defence of the plants against insects by toxins formed in the plants, in particular those formed in the plants by the genetic material from
Bacillus thuringiensis (for example by the genes CryΙA(a), CryIA(b), CryΙA(c), CryDA, CrylDA,
CryDIB2, Cry9c, Cry2Ab, Cry3Bb and CrylF and also combinations thereof) (hereinbelow referred to as "Bt plants"). Traits that are also particularly emphasized are the increased defence of the plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits that are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinothricin (for example the "PAT" gene). The genes which impart the desired traits in each case can also be present in combinations with one another in the transgenic plants. Examples of "Bt plants" which may be mentioned are maize varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade names YIELD GARD® (for example maize, cotton, soya beans), KnockOut® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may be mentioned are maize varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soya bean), Liberty Link® (tolerance to phosphinothricin, for example oilseed rape), Evil® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example maize). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned include the varieties sold under the name Clearfield® (for example maize). Of course, these statements also apply to plant cultivars having these genetic traits or genetic traits still to be developed, which plants will be developed and/or marketed in the future.
The plants listed can be treated according to the invention in a particularly advantageous manner with the compounds of the general formula (I) or the active compound mixtures according to the invention, where in addition to the good control of weed plants, the above-mentioned synergistic effects with the transgenic plants or plant cultivars occur. The preferred ranges stated above for the active compounds or mixtures also apply to the treatment of these plants. Particular emphasis is given to the treatment of plants with the compounds or mixtures specifically mentioned in the present text.
Then the preparation and application of the compounds of the formula (I) according to the present invention, will be described more specifically by the following examples. The present invention, however, should not be restricted only to them in any way. Synthesis Example 1
Figure imgf000018_0001
2,2-Bis(chloromethyl)propanoyl chloride (0.34g) was dissolved in THF (5ml) and added dropwise to a solution of 5-N-methylamino- 3-(3-trifluoromethylphenyl)-4-thiazolidinone (0.50 g) and tri- ethylamine (0.18g) in THF (10ml) at room temperature and the mixed solution was stirred for 3 hours. After the reaction, cold water was added to the reaction mixture, and the reaction mixture was extracted with ethyl acetate (50ml), washed with a saturated aqueous solution of sodium chloride, and dried over anhydrous magnesium sulfate. The residue, obtained by distilling off ethyl acetate, was purified by silica gel column chromatography (eluent: ethyl acetate: hexane =1:1) to obtain the objective 5-{2,2-bis(chloromemyl)propanoyl-N-memyl}amino-3-(3-trifluoromethylphenyl)-4- thiazolidinone (0.64 g).
mp: 115 to ll6°C
The compounds obtained by the preparation process of the compounds of the formula (I) according to the present invention exemplified in the above-mentioned Synthesis Example 1, are shown, together with the compound synthesized in Synthesis Example 1, in the following Table 1.
Examples of the compounds, in case that the compounds of the formula (I) of the present invention are represented by the formula
Figure imgf000018_0002
are shown in Table 1.
In Table 1 Me represents methyl and t-Bu represents tert-butyl. Table 1
Figure imgf000019_0001
Comp. No. Ra Rb Rc Rd Re Rf X mp(°C)or nD 20 1 F H F Me Me CH2F S 2 F H F Me Me • CHC12 S 3 F H F Me CH2C1 CH2C1 S 4 F H F Me Me CHC12 CH2 5 F H F Me CH2F CH2F CH2 6 F H F Me CH2C1 CH2C1 CH2 7 F H F Me CH2C1 CH2C1 O
Figure imgf000019_0002
9 F F H Me Me CH2C1 S 10 F F H Me Me CHC12 S 1.5690 11 F F H Me CH2C1 CH2C1 S 101-104 12 F F H Me Me CHC12 CH2 13 F F H Me CH2C1 CHC12 CH2 14 F F H Me CH2C1 CH2C1 CH2 15 F F H Me Me CHaF O 16 F F H Me CH2C1 CH2C1 O 17 F F F Me Me CHC12 S
Figure imgf000019_0003
19 F F F Me CH2C1 CH2C1 s 20 F F F Me Me CHC12 CH2 21 F F F Me CH2C1 CH2C1 CH2 22 F F F CH2F CH2F CH^F CH2 23 F F F Me Me CH2C1 O 24 F F F Me CH2C1 CH2C1 O 25 F Me CI Me Me CHC12 s 26 F Me CI Me CH2C1 CH2C1 s 27 F Me CI Me CH2C1 CHC12 s Comp. No. Ra Rb R° Rd Re Rf X mp(°C)or nD 20 28 F Me CI Me Me CH2F CH2 29 F Me CI Me Me CHC12 CH2 30 F Me CI Me CH2C1 CH2C1 CH2 31 F Me CI Me Me CHC12 0 32 F Me CI Me CH2C1 CH2C1 0 33 CI H H Me Me CHC12 s 34 CI H H Me CH2CI CH2C1 s 35 CI H H CH2F CH2F CHzF s 36 CI H H Me Me CH2C1 CH2 37 CI H H Me Me CHC12 CH2 38 CI H H Me CH2C1 CH2C1 CH2 39 CI H H Me CH2F CH2F O 40 CI H H Me CH2C1 CH2C1 0 41 CI H CI Me Me CH2F s 42 CI H CI Me Me CHC12 s 1.5740 43 CI H CI Me CH2C1 CH2C1 s 1.5411 44 CI H CI Me Me CHC12 CH2 1.5600 45 CI H CI Me CH2F CH2F CH2 46 CI H CI Me CH2C1 CH2C1 CH2 1.5600 47 CI H CI Me CH2C1 CH2C1 0 48 CI H CI Me CH2C1 CHCI2 O 49 CI F H Me Me CH2F s 1.5250 50 CI F H Me Me CH2C1 s 51 CI F H Me Me CHCI2 s 1.5765 52 CI F H Me CH2F CH2F s 1.5290 53 CI F H Me CH2C1 CI s 54 CI F H Me CH2C1 CH2CI s 123-125 55 CI F H Me CH2C1 CHCI2 s 56 CI F H Me CH2Br Br s 57 CI F H CH2F CHaF CH2F s 137-139 58 CI F H CH2C1 CH2C1 CH2C1 s 59 CI F H Me Me CHaF CH2 1.5125 60 CI F H Me Me CH2C1 CH2 61 CI F H Me Me CHCI2 CH2 125-127 Comp. No. Ra R Rc Rd Re Rf X mp(°C)or nD 20 62 CI F H Me CH2F CH2F CH2 83-86 63 CI F H Me CH2C1 CI CH2 64 CI F H Me CH2C1 CH2C1 CH2 1.5455 65 CI F H Me CH2C1 CHC12 CH2 66 CI F H Me CH2Br Br CH2 67 CI F H CH2F CH2F CH2F CH2 103-105 68 CI F H CH2C1 CH2C1 CH2C1 CH2 69 CI F H Me Me CH2F O 70 CI F H Me Me CH2C1 O 71 CI F H Me Me CHCI2 O 72 CI F H Me CH2F CH2F O 73 CI F H Me CH2C1 CI O 74 CI F H Me CH2C1 CH2C1 O 75 CI F H Me CH2C1 CHC12 O 76 CI F H Me CH2Br Br O 77 CI F H CH2F CH2F CH2F O 78 CI F H CH2C1 CH2C1 CH2CI O 79 CI F CI Me Me CH2C1 s 80 CI F CI Me Me CHC12 s 81 CI F CI Me CH2C1 CH2C1 s 82 CI F CI Me Me CHC12 CH2 83 CI F CI Me CH2C1 CH2C1 CH2 84 CI F CI Me CH2C1 CHC12 CH2 85 CI F CI Me CH2C1 CH2C1 O 86 CI F CI CH2F CH2F CH2F O 87 CI CI H Me Me CHC12 s 1.5440 88 CI CI H Me CH2F CH2F s 89 CI CI H Me CH2C1 CH2C1 s 176-177 90 CI CI H Me Me CHC12 CH2 136 91 CI CI H Me CH2C1 CH2C1 CH2 126 92 CI CI H CH2F CH2F CH2F CH2 93 CI CI H Me Me CH2F O 94 CI CI H Me CH2C1 CH2C1 O 95 CI CI CI Me Me CHCI2 s 1.5905 Comp. No. Ra Rb Rc Rd Re Rf X mp(°C)or nD 20 96 CI CI CI Me CH2C1 CH2C1 s 1.5730 97 CI CI CI Me CH2C1 CHC12 s 98 CI CI CI Me Me CH2F CH2 99 CI CI CI Me Me CHC12 CH2 100 CI CI CI Me CH2C1 CH2C1 CH2 101 CI CI CI Me Me CH2C1 0 102 CI CI CI Me CH2C1 CH2C1 0 . 103 CI Me H Me Me CHC12 s 1.5665 104 CI Me H Me CH2C1 CH2C1 s 151-153 105 CI Me H CH2F CH2F CH2F s 106 CI Me H Me Me CH2C1 CH2 107 CI Me H Me Me CHC12 CH2 132-133 108 CI Me H Me CH2C1 CH2C1 CH2 140-141 109 CI Me H Me Me CHC12 0 110 CI Me H Me CH2C1 CH2C1 O 111 CI OCH3 H Me Me CH2F s 112 CI OCH3 H Me Me CHCI2 s 1.5760 113 CI OCH3 H Me CH2C1 CH2C1 s 161-163 114 CI OCH3 H Me Me CHCI2 CH2 115 CI OCH3 H Me CH2F CH2F CH2 116 CI OCH3 H Me CH2C1 CH2C1 CH2 117 CI OCH3 H Me CH2F CH2F 0 118 CI OCH3 H Me CH2C1 CH2C1 0 119 CI CF3 H Me Me CH2C1 s .
Figure imgf000022_0001
121 CI CF3 H Me CH2C1 CH2C1 s 122 CI CF3 H Me Me CHC12 CH2 123 CI CF3 H Me CH2C1 CH2C1 CH2 124 CI CF3 H Me CH2C1 CHCI2 CH2 125 CI CF3 H Me CH2C1 CH2C1 0 126 CI CF3 H Me CH2C1 CHC12 0
Figure imgf000022_0002
128 Br F H Me CH2F CH2F s 129 Br F H Me CH2C1 CH2C1 s Comp. No. Ra Rb Rc Rd Re Rf X mp(°C)or nD 20 130 Br F H Me Me CHC12 CH2 131 Br F H Me CH2C1 CH2C1 CH2 132 Br F H CH2F CH2F CH2F CH2 133 Br F H Me CH2C1 CH2C1 O 134 Br F H CH2F CHzF CH2F 0 135 Br Me H Me Me CHC12 s 136 Br Me H Me CH2C1 CH2C1 s 137 Br Me H CH2F CH2F CH2F s 138 Br Me H Me Me CH2F CH2 139 Br Me H Me Me CHC12 CH2 140 Br Me H Me CH2C1 CH2C1 CH2 141 Br Me H Me Me CH2F O 142 Br Me H Me CH2C1 CH2C1 O 143 Me CI H Me Me CH2F s 144 Me CI H Me Me CHC12 s 145 Me CI H Me CH2C1 CH2C1 s 146 Me CI H Me Me CH2C1 CH2
Figure imgf000023_0001
148 Me CI H Me CH2C1 CH2C1 CH2 149 Me CI H Me Me CH2C1 O 150 Me CI H Me CH2C1 CH2C1 O 151 OCH3 CI H Me Me CH2C1 s 152 OCH3 CI H Me Me CHC12 s 153 OCH3 CI H Me CH2C1 CH2C1 s 154 OCH3 CI H Me Me CHCI2 CH2 155 OCH3 CI H Me CH2F CH2F CH2 156 OCH3 CI H Me CH2C1 CH2C1 CH2 157 OCH3 CI H Me CH2C1 CH2C1 O
Figure imgf000023_0002
160 OCH3 Me H Me CH2F CH2F s 161 OCH3 Me H Me CH2C1 CH2C1 s 162 OCH3 Me H Me Me CHCI2 CH2 101-113 163 OCH3 Me H Me CH2C1 CH2C1 CH2 133-143 Comp. No. Ra Rb Rc Rd Re Rf X mp(°C)or nD 20 164 OCH3 Me H Me CH2C1 CHC12 CH2 165 OCH3 Me H Me CH2F CH2F O 166 OCH3 Me H Me CH2C1 CH2C1 O 167 CF3 H H t-Bu H Br s 125-130 168 CF3 H H Me Me CH2F s 1.5312 169 CF3 H H Me Me CH2C1 s 72-76 170 CF3 H H Me Me CHC12 s 73-77 171 CF3 H H Me CH2F CH2F s 1.5185 172 CF3 H H Me CH2C1 CI s 173 CF3 H H Me CH2C1 CH2C1 s 115-116 174 CF3 H H Me CH2C1 CHC12 s 1.5510 175 CF3 H H Me CH2Br Br s 176 CF3 H H CH2F CH2F CH2F s 1.5170 177 CF3 H H CH2C1 CH2C1 CH2C1 s 161-163 178 CF3 H H t-Bu H Br CH2 102-104 179 CF3 H H Me Me CH2F CH2 101-103 180 CF3 H H Me Me CH2C1 CH2 82-84 181 CF3 H H Me Me CHCI2 CH2 106-107 182 CF3 H H Me CH2F CH2F CH2 1.5185 183 CF3 H H Me CH2C1 CI CH2 184 CF3 H H Me CH2C1 CH2C1 CH2 70-71 185 CF3 H H Me CH2C1 CHC12 CH2 1.5350 186 CF3 H H Me CH2Br Br CH2 187 CF3 H H CH2F CHzF CH2F CH2 1.4990 188 CF3 H H CH2C1 CH2C1 CH2C1 CH2 1.5270 189 CF3 H H t-Bu H Br O 190 CF3 H H Me Me CH2F O 191 CF3 H H Me Me CH2C1 O 1.5190
Figure imgf000024_0001
193 CF3 H H Me CH2F CH2F O 194 CF3 H H Me CH2C1 CI O 195 CF3 H H Me CH2C1 CH2C1 O 1.5270 196 CF3 H H Me CH2C1 CHCI2 O 197 CF3 H H Me CH2Br Br O Comp. No. Ra Rb Rc Rd Re Rf X mp(°C)or nD 20 198 CF3 H H CH2F CH2F CH2F 0 199 CF3 H H CH2C1 CH2C1 CH2C1 0 200 CF3 H OCH3 Me Me CHC12 s 201 CF3 H OCH3 Me CH2C1 CH2C1 s 202 CF3 H OCH3 Me CH2C1 CHC12 s 203 CF3 H OCH3 Me Me CHC12 CH2 204 CF3 H OCH3 Me CH2C1 CH2C1 CH2 205 CF3 H OCH3 CH2F CH2F CH2F CH2 206 CF3 H OCH3 Me CH2C1 CH2C1 O 207 CF3 H OCH3 Me CH2C1 CHC12 O 208 CF3 H CF3 Me Me CHC12 s 209 CF3 H CF3 Me CH2C1 CH2C1 s 210 CF3 H CF3 CH2F CH2F CH2F s 211 CF3 H CF3 Me Me CH2F CH2 212 CF3 H CF3 Me Me CHC12 CH2 213 CF3 H CF3 Me CH2C1 CH2C1 CH2 214 CF3 H CF3 Me CH2C1 CH2C1 O 215 CF3 H CF3 CH2F CH2F CH2F O 216 CF3 F H Me Me CH2F s 217 CF3 F H Me Me CHC12 s 1.5330 218 CF3 F H Me CH2C1 CH2C1 s 103-105 219 CF3 F H Me Me CH2C1 CH2 220 CF3 F H Me Me CHC12 CH2 1.5150 221 CF3 F H Me CH2C1 CH2C1 CH2 1.5208 222 1 CF3 F H Me Me CH2F O 223 CF3 F H Me CH2C1 CH2C1 O 224 CF3 CI H Me Me CH2C1 s 225 CF3 CI H Me Me CHCI2 s 124-125 226 CF3 CI H Me CH2C1 CH2C1 s 161-162 227 CF3 CI H Me Me CHCI2 CH2 1.5465 228 CF3 CI H Me CH2F CH2F CH2 229 CF3 CI H Me CH2C1 CH2C1 CH2 124 230 CF3 CI H Me Me CH2C1 O 231 CF3 CI H Me CH2C1 CH2C1 O Comp. No. Ra Rb Rc Rd Re Rf X mp(°C)ornD 20 232 CF3 CF3 H Me Me CHC12 S 233 CF3 CF3 H Me CH2F CH2F s 234 CF3 CF3 H Me CH2C1 CH2C1 s 235 CF3 CF3 H Me Me CHCI2 CH2 236 CF3 CF3 H Me CH2C1 CH2C1 CH2 237 CF3 CF3 H Me CH2C1 CHCI2 CH2
Figure imgf000026_0001
239 CF3 CF3 H Me CH2C1 CH2C1 O 240 CF2C1 H H Me Me CHC12 s 241 CF2C1 H H Me CH2C1 CH2C1 s 242 CF2C1 H H Me CH2C1 CHC12 s 243 CF2C1 H H Me Me CHC12 CH2 244 CF2C1 H H Me CH2C1 CH2C1 CH2 245 CF2C1 H H CH2F CH2F CH2F CH2 246 CF2C1 H H Me CH2F CH2F O 247 CF2C1 H H Me CH2C1 CH2C1 O 248 CC13 H H Me Me CHC12 s 249 CC13 H H Me CH2C1 CH2C1 s 250 CC13 H H CH2F CH2F CH2F s 251 CC13 H H Me Me CH2F CH2 252 CC13 H H Me Me CHC12 CH2 253 CC13 H H Me CH2C1 CH2C1 CH2 254 CC13 H H Me CH2C1 CH2C1 O 255 CC13 H H Me CH2C1 CHC12 O 256 OCHF2 H H Me Me CH2F s 257 OCHF2 H H Me Me CHCI2 s 258 OCHF2 H H Me CH2C1 CH2C1 s 259 OCHF2 H H Me Me CH2F CH2 1.5200 260 OCHF2 H H Me Me CH2C1 CH2 261 OCHF2 H H Me Me CHCI2 CH2 1.5415 262 OCHF2 H H Me CH2F CH2F CH2 100-101 263 OCHF2 H H Me CH2C1 CH2C1 CH2 127-130 264 OCHF2 H H Me CH2C1 CHCI2 CH2 265 OCHF2 H H CH2F CH2F CH2F CH2 1.5135 Comp. No. Ra Rb Rc Rd Re Rf X mp(°C)or nD 20 266 OCHF2 H H CH2C1 CH2C1 CH2C1 CH2 267 OCHF2 H H Me CH2C1 CH2C1 O 268 OCHF2 H H CH2F CH2F CHiF O 269 OCF3 H H Me Me CH2F S 77-78 270 OCF3 H H Me Me CH2C1 S 271 OCF3 H H Me Me CHCI2 S 1.5180 272 OCF3 H H Me CH2F CH2F S 85-87 273 OCF3 H H Me CH2C1 CI s 274 OCF3 H H Me CH2C1 CH2C1 s 1.5245 275 OCF3 H H Me CH2C1 CHCI2 s 276 OCF3 H H Me CH2Br Br s 277 OCF3 H H CH2F CH2F CH2F s 94-95 278 OCF3 H H CH2C1 CH2C1 CH2C1 s 279 OCF3 H H Me Me CH2F CH2 68-72 280 OCF3 H H Me Me CH2C1 CH2 281 OCF3 H H Me Me CHCI2 CH2 1.5180 282 OCF3 H H Me CH2F CHϊF CH2 95-96 283 OCF3 H H Me CH2C1 CI CH2 284 OCF3 H H Me CH2C1 CH2C1 CH2 1.5150 285 OCF3 H H Me CH2C1 CHC12 CH2 286 OCF3 H H Me CH2Br Br CH2 287 OCF3 H H CH2F CH2F CH2F CH2 85 288 OCF3 H H CH2C1 CH2C1 CH2C1 CH2 289 OCF3 H H Me Me CH2F O 290 OCF3 H H Me Me CH2C1 O
Figure imgf000027_0001
292 OCF3 H H Me CH2F CH2F O 293 OCF3 H H Me CH2C1 CI O 294 OCF3 H H Me CH2C1 CH2C1 O 295 OCF3 H H Me CH2C1 CHC12 O 296 OCF3 H H Me CH2Br Br O 297 OCF3 H H CH2F CH2F CH2F O 298 OCF3 H H CH2C1 CH2C1 CH2C1 O 299 OCF3 F H Me Me CH2C1 s Comp. No. Ra Rb Rc Rd Re Rf X mp(°C)ornD 20 300 OCF3 F H Me Me CHC12 S 301 OCF3 F H Me CH2C1 CH2C1 S 302 OCF3 F H Me Me CH2F CH2 303 OCF3 F H Me Me CHCI2 CH2 304 OCF3 F H Me CH2C1 CH2CI CH2 305 OCF3 F H Me Me CH2F O 306 OCF3 F H Me CH2C1 CH2C1 O 307 OCF2Cl H H Me Me CH2CI S 308 OCF2CI H H Me CH2F CH2F S 309 OCF2CI H H Me CH2C1 CH2C1 S 310 OCF2Cl H H Me Me CH2C1 CH2 311 OCF2Cl H H Me Me CHC12 CH2 312 OCF2Cl H H Me CH2C1 CH2C1 CH2 313 OCF2Cl H H Me Me CH2C1 O 314 OCF2Cl H H Me CH2C1 CH2C1 O 315 OCH2CF3 H H Me Me CHC12 S 316 OCH2CF3 H H Me CH2C1 CH2C1 s 317 OCH2CF3 H H Me CH2C1 CHC12 s 318 OCH2CF3 H H Me Me CHC12 CH2 319 OCH2CF3 H H Me CH2F CH2F CH2 320 OCH2CF3 H H Me CH2C1 CH2C1 CH2 321 OCH2CF3 H H Me Me CHC12 O 322 OCH2CF3 H H Me CH2C1 CH2C1 O 323 OCHCl2 H H Me Me CHC12 s 324 OCHCl2 H H Me CH2C1 CH2C1 s 325 OCHCl2 H H CH2F CH2F CH2F s 326 OCHCl2 H H Me Me CHC12 CH2 327 OCHCl2 H H Me CH2C1 CH2C1 CH2 328 OCHCl2 H H Me CH2C1 CHCI2 CH2 329 OCHCl2 H H Me CH2F CHzF O 330 OCHCl2 H H Me CH2C1 CH2C1 O 331 SCHF2 H H Me Me CH2CI s
Figure imgf000028_0001
333 SCHF2 H H Me CH2C1 CH2C1 s Comp. No. Ra Rb R° Rd Re Rf X mp(°C)or nD 20 334 SCHF2 H H Me Me CH2F CH2 335 SCHF2 H H Me Me CHC12 CH2 336 SCHF2 H H Me CH2C1 CH2C1 CH2 337 SCF3 H H Me Me CH2F S 101-102 338 SCF3 H H Me Me CH2C1 S 339 SCF3 H H Me Me CHC12 s 1.5411 340 SCF3 H H Me CH2F CH2F s 88-92 341 SCF3 H H Me CH2C1 CH2C1 s 1.5400 342 SCF3 H H Me CH2C1 CHC12 s 343 SCF3 H H CH2F CH2F CH2F s 116-117 344 SCF3 H H Me Me CH2C1 CH2 345 SCF3 H H Me Me CHCI2 CH2 1.5129 346 SCF3 H H Me CH2C1 CH2C1 CH2 1.5322 347 OCF2O H Me Me CHCI2 s 1.5462 348 OCF2O H Me CH2F CH2F s 349 OCF20 H Me CH2C1 CH2C1 s 84-89 350 OCF2O H Me Me CHCI2 CH2 351 OCF2O H Me CH2F CHΪF CH2 1.5360 352 OCF2O H Me CH2C1 CH2C1 CH2 1.5270 353 OCF2O H Me Me CH2C1 O 354 OCF2O H Me CH2C1 CH2C1 O 355 OCF2CF20 H Me Me CHCI2 s 111-117 356 OCF2CF20 H Me CH2C1 CH2C1 s 120-123 357 OCF2CF20 H Me CH2C1 CHCI2 s 358 OCF2CF20 H Me Me CHCI2 CH2 130-132 359 OCF2CF20 H Me CH2C1 CH2CI CH2 92-96 360 OCF2CF20 H Me CH2C1 CHCI2 CH2 361 OCF2CF20 H Me Me CHCI2 O 362 OCF2CF20 H Me CH2C1 CH2C1 O Synthesis Example 2 (Preparation of intermediate)
Figure imgf000030_0001
5-chloro-3-(3-trifluoromethylphenyl)- 4-thiazolidinone (11.0 g) was dissolved in dichloromethane (30ml) and added dropwise to a mixed solution of 40% aqueous solution of methylamine (45.5 g), sodium iodide (0.59 g), triethylbenzylammonium chloride (0.89 g) and dichloromethane (30 ml) with ice bath cooling. The mixture was stirred for 1 hour with ice bath cooling. After the reaction, the reaction mixture was extracted with dichloromethane (50 ml), washed with saturated aqueous solution of sodium chloride, and dried over anhydrous magnesium sulfate. The residue, obtained by distilling off dichloromethane, was purified by silica gel column chromatography (eluent: ethyl acetate: hexane =1:1 to 2:1) to obtain 5-N-methylamino- 3-(3-trifluoromethylphenyl)-4-thia- zolidinone (5.80g).
mp: 88-89°C
Test Example 1: Test for herbicidal activity against paddy field weeds
Preparation of formulation of the active compound
Carrier: Dimethylformamide (DMF) 5 parts by weight
Emulsifier: Benzyloxy polyglycol ether 1 part by weight
A formulation of an active substance is obtained as an emulsifiable concentrate by mixing 1 part by weight of the active compound with the above-mentioned amount of the carrier and emulsifier. A prescribed amount of the formulation is diluted with water.
Test method
In a greenhouse three seedlings of paddy rice (variety: Nihonbare) of 2.5 leaf stage (15cm tall) were transplanted in a 500cm2 pot filled with paddy field soil. Then seeds or tubers of Echinochloa crusgάlli, Cyperus difformis L, Scirpus juncoides Roxburgh, Monochoria vaginalis Presl, broad-leaved weeds (Lindernia procumbens Philcox, Rotala indica Koehne, Elatine triandra Schk, Ammannia multiflora Roxb., Dopatrium junceum Hammilt ,etc), Cyperus serotinus Rottboel and Sagittaria pygmaea Miq were inoculated and water was poured to a depth of about 2 to 3 cm.
Five days after the rice transplantation, a diluted solution of each formulation of active compound prepared according to the aforementioned preparation method was applied to the surface of water. After the treatment the water depth of 3 cm was maintained and the herbicidal activity was examined after 3 weeks from the treatment. The herbicidal activity was rated 100% in the case of complete death and as 0% in the case of no herbicidal activity.
Results
As a result, the compounds of examples No. 11, 49, 51, 52, 54, 57, 61, 168, 171, 176, 269 and 277 showed a sufficient herbicidal activity against paddy field weeds at the application rate (amount of the active component) of 0.125kg/ha and a safety to the transplanted paddy rice. Test Example 2: Test of pre-emergence soil treatment against field weeds
Test method
In a greenhouse, on the surface layer of a 120cm2 pot filled with field soil, seeds of Echinochloa crusgalli, Setaria viridis, Amaranthus retroflexus and Polygonum were sown and covered with soil. A diluted solution of the prescribed chemical amount prepared in the same manner as in the above-mentioned Test Example 1 was sprayed uniformly on the soil surface layer of each test pot.
The rate of herbicidal activity was examined 4 weeks after the treatment.
Results
As a result, the compounds of examples No. 168, 171, 176, 261 and 281 showed herbicidal activity of higher than 90% against Echinochloa crusgalli, Setaria viridis, Amaranthus retroflexus and Polygonum at the application rate (amount of the active component) of 0.06kg/ha.
Test Example 3: Test of post-emergence foliage treatment against field weeds
Test method
hi a greenhouse, seeds of Echinochloa crusgalli, Setaria viridis, Amaranthus retroflexus and Polygonum were sown in a 120cm2 pot filled with field soil and covered with soil. Ten days after the sowing and soil covering (weeds were 2-leaf stage in average) a diluted solution of the prescribed chemical amount prepared in the same manner as in the above-mentioned Test Example 1 was sprayed uniformly on the foliage part in each test pot. The rate of herbicidal activity was examined 3 weeks after the treatment.
Results
As a result, the compounds of examples No. 45, 61, 265 and 281 showed herbicidal activity of higher than 90% against Echinochloa crusgalli, Setaria viridis, Amaranthus retroflexus and Polygonum at the application rate (amount of the effective component) of 0.5kg/ha. Formulation Example 1 (Granule)
To a mixture of the compound of the present invention No. 52 (10 parts), bentonite (mont- morillonite) (30 parts), talc (58 parts) and ligmnsulfonate salt (2 parts), water (25 parts) were added, well kneaded, made into granules of 10 to 40 mesh by an extrusion granulator and dried at 40 to 50°C to obtain granules.
Formulation Example 2 (Granules)
Clay mineral particles (95 parts) having particle diameter distribution in the range of 0.2 to 2mm are put in a rotary mixer. While rotating it, the compound of the present invention No.49 (5 parts) is sprayed together with a liquid diluent, wetted uniformly and dried at 40 to 50°C to obtain granules.
Formulation Example 3 (Emulsifiable concentrate)
The compound of the present invention No. 261 (30 parts), xylene (5 parts), polyoxyethylene alkyl phenyl ether (8 parts) and calcium alkylbenzenesulfonate (7 parts) are mixed and stirred to obtain an emulsifiable concentrate.
Formulation Example 4 (Wettable powder)
The compound of the present invention No. 281 (15 Parts), a mixture of white carbon (hydrous amorphous silicon oxide fine powders) and powder clay (1:5) (80 parts), sodium alkylbenzenesulfonate (2 parts) and sodium alkylnaphthalenesulfonate-formalin-condensate (3 parts) are crushed and mixed to make a wettable powder.
Formulation Example 5 (Water dispersible granule)
The compound of the present invention No. 176 (20 Parts), sodium ligmnsulfonate (30 parts), bentonite (15 parts) and calcined diatomaceous earth (35 parts) are well mixed, added with water, extruded with 0.3mm screen and dried to obtain water dispersible granules.

Claims

Claims
1. Novel azolidine derivatives of the formula
Figure imgf000034_0001
wherein
R1 represents halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, haloalkylthio or halo- alkylenedioxy, m represents 0, 1,
2, 3, 4 or 5, the R1 substituents are identical or different, when m represents 2,
3, 4 or 5,
R2 represents alkyl,
X represents alkylidene, an oxygen atom or a sulfur atom, and represents one of the groups
Figure imgf000034_0002
Figure imgf000034_0003
Q-hal
Figure imgf000034_0004
Q
Figure imgf000035_0001
or Q
-C- Hal (A-5), H
wherein
Q represents alkyl,
Q-hal represents haloalkyl, and
Hal represents halogen.
Compounds according to Claim 1 wherein
R1 represents fluoro, chloro, bromo,
Figure imgf000035_0002
C1. haloalkyl, Ci.-Jialo- alkoxy, Cι_4haloalkylthio or Cι.4haloa_kylenedioxy,
m represents 1, 2 or 3,
R represents methyl,
X represents methylene, an oxygen atom or a sulfur atom, and represents one of the groups
Figure imgf000035_0003
Figure imgf000035_0004
Q-hal
Figure imgf000036_0001
Figure imgf000036_0002
or Q
-C- Hal (A-5), H
wherein
Q represents C^alkyl,
Q-hal represents
Figure imgf000036_0003
and
Hal represents chloro or bromo.
Compounds according to Claim 1 or 2 wherein
R1 represents fluoro, chloro, bromo, methyl, methoxy, trifluoromethyl, chlorodifluoromethyl, trichloromethyl, difluoromethoxy, chlorodifluoromethoxy, trifluoro- methoxy, trifluoroethoxy, dichloromethoxy, difluoromethylthio, trifluoromethyl- thio, difluoromethylenedioxy or tetrafluoroethylenedioxy,
m represents 1, 2 or 3,
R1 connects to the 3-position of the phenyl group, when m represents 1,
two R1 substituents connect to the 3-position and 4-position, or connect to the 3-position and 5-position of the phenyl group, and two R1 substituents are identical or different, when m represents 2,
three R1 substituents connect to the 3-position,
4-position and 5-position of the phenyl group, and three R1 substituents are identical or different, when m represents 3, R2 represents methyl,
X represents methylene, an oxygen atom or a sulfur atom, and
A represents one of the groups
Figure imgf000037_0001
Figure imgf000037_0002
Figure imgf000037_0003
Q
Figure imgf000037_0004
or Q
-C- Hal (A-5), H
wherein represents methyl or tert-butyl,
Q-hal represents fluoromethyl, chloromethyl, dichloromethyl or bromomethyl, and
Hal represents chloro or bromo. A process for the preparation of the compounds of the formula (I)
Figure imgf000038_0001
wherein
R1, m, R2, A and X have the same definition as aforementioned in claim 1, characterized in that a) compounds of the formula (D)
Figure imgf000038_0002
wherein
R1, m, R2 and X have the same definition as aforementioned, are reacted with compounds of the formula (ID)
Figure imgf000038_0003
wherein
M represents a halogen or a hydroxyl group, and
A has the same definition as aforementioned, in the presence of inert solvents, and if appropriate, in the presence of an acid binding agent or a condensing agent.
5. Herbicidal composition, characterized in that they contain at least one azolidine derivatives of the formula (I) according to claim 1.
6. Process for combating weeds, characterized in that an azolidine derivative of the formula (I) according to claim 1 is allowed to act on weeds and/or their habitat.
7. Use of an azolidine derivative of the formula (I) according to claim 1 for combating weeds.
8. Process for the preparation of herbicidal compositions, characterized in that an azolidine derivative of the formula (I) according to claim 1 is mixed with extenders and/or surface active agents.
PCT/EP2004/006367 2003-06-26 2004-06-14 Lazolidine derivatives as herbicidal agents WO2005000824A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995033719A1 (en) * 1994-06-02 1995-12-14 Zeneca Limited Substituted pyrrolidone, thiazolidones or oxazolidones as herbicides
WO1997020838A1 (en) * 1995-12-01 1997-06-12 Zeneca Limited Substituted pyrrolidinone, thiazolidinone or oxazolidinone as herbicides
WO2000021928A1 (en) * 1998-10-09 2000-04-20 Syngenta Limited Substituted pyrrolidinone, thiazolidinone or oxazolidinone as herbicides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995033719A1 (en) * 1994-06-02 1995-12-14 Zeneca Limited Substituted pyrrolidone, thiazolidones or oxazolidones as herbicides
WO1997020838A1 (en) * 1995-12-01 1997-06-12 Zeneca Limited Substituted pyrrolidinone, thiazolidinone or oxazolidinone as herbicides
WO2000021928A1 (en) * 1998-10-09 2000-04-20 Syngenta Limited Substituted pyrrolidinone, thiazolidinone or oxazolidinone as herbicides

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