WO2006102986A1 - A use of cyclohexanedione derivatives as herbicide - Google Patents

A use of cyclohexanedione derivatives as herbicide Download PDF

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Publication number
WO2006102986A1
WO2006102986A1 PCT/EP2006/002306 EP2006002306W WO2006102986A1 WO 2006102986 A1 WO2006102986 A1 WO 2006102986A1 EP 2006002306 W EP2006002306 W EP 2006002306W WO 2006102986 A1 WO2006102986 A1 WO 2006102986A1
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methyl
represent
represent hydrogen
nonyl
case
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PCT/EP2006/002306
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French (fr)
Inventor
Akihiko Yanagi
Shinichi Narabu
Yasushi Yoneta
Keiji Endo
Shinichi Shirakura
Shin Nakamura
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Bayer Cropscience Ag
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Priority to JP2008503395A priority Critical patent/JP2008534532A/en
Publication of WO2006102986A1 publication Critical patent/WO2006102986A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/708—Ethers
    • C07C69/712—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • 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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/385—Saturated compounds containing a keto group being part of a ring
    • C07C49/403—Saturated compounds containing a keto group being part of a ring of a six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/703—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups
    • C07C49/713—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups a keto group being part of a six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/703—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups
    • C07C49/723—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups polycyclic
    • C07C49/727—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups polycyclic a keto group being part of a condensed ring system
    • C07C49/733—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups polycyclic a keto group being part of a condensed ring system having two rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
    • C07C69/24—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with monohydroxylic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the present invention relates to a use of cyclohexanedione derivatives as herbicide, to novel cyclohexanedione derivatives, to a process for their preparation, to novel intermediates, and to mixed herbicidal compositions.
  • R 1 represents C ⁇ -galkyl that may be optionally Ci -4 alkoxy-substituted or C 6-9 alkenyl that may be optionally C-i ⁇ alkoxy-substituted,
  • R 2 , R 3 , R 6 and R 7 represent hydrogen or methyl
  • R 2 forms ethylene together with R 7 , and
  • R 4 and R 5 represent hydrogen or methyl, or together represent oxo.
  • R 1A represents C h alky! that may be optionally C-
  • R 2A , R 3A , R 6A and R 7A represent hydrogen or methyl
  • R 2A forms ethylene together with R 7A , and
  • R 4A and R 5A represent hydrogen or methyl, or together represent oxo, provided that the following cases (i) - (iii) are excluded: (i) the case in which R 2A , R 3A , R 4A , R 5A , R 6A and R 7A represent hydrogen and R 1A represents n-hexyl, n-heptyl or n-nonyl, (ii) the case in which R 2A , R 3A , R 6A and R 7A represent hydrogen, R 4A and R 5A represent methyl and R 1A represents n-hexyl, n-heptyl or n-nonyl, (iii) the case in which R 2A , R 3A , R 6A and R 7A represent methyl, R 4A and R 5A together represent oxo and R 1A represents n-nonyl.
  • the compounds of the formula (IA) can be obtained by a process in which
  • R 1A , R 2A , R 3A , R 4A , R 5A , R 6A and R 7A have the same definition as aforementioned, are reacted to a rearrangement in the presence of innert solvents, and if appropriate, in the presence of an acid binder, and if appropriate, in the presence of a cyanide, and if appropriate, in the presence of a phase-transfer catalyst.
  • the compounds of the aforementioned formula (I) can also be prepared by the above-mentioned preparation process (a).
  • the cyclohexanedione derivatives of the formula (I), according to the present invention which include the novel compounds of the formula (IA) show strong herbicidal action.
  • the cyclohexanedione derivatives of the formula (I) are partly and generically embraced by the general formula described in U.S. Patent Specification No. 4202840, they are not specifically described in said U.S. Patent.
  • the cyclohexanedione derivatives of the formula (I) include the known compounds described in WO 03/51806 and Flavour and Fragrance Journal, Vol.15 (4), p.278-280, 2000, Journal of Chemical Ecology, Vol.
  • cyclohexanedione derivatives of the formula (I), according to the present invention unexpectedly show very excellent quickly effective herbicidal action, compared with the known compounds described in the above-mentioned U.S. Patent.
  • cyclohexanedione derivatives of the formula (I), according to the present invention show, as specifically mentioned later, even stronger herbicidal action as mixed herbicidal compositions by mixing with other herbicidally active compounds.
  • C ⁇ -galkyl can be straight-chain or branched-chain. There can be mentioned, for example, n-hexyl, n-heptyl, n-octyl, 1-methylheptyl, n-nonyl, 3-methyloctyl, 7-methyloctyl, etc.
  • Ce- ⁇ alkenyl there can be mentioned, for example, 6-nonenyl, etc.
  • C-i-4alkoxy there can be mentioned, for example, methoxy, ethoxy, etc.
  • R 1A represents C 6-9 alkyl that may be optionally methoxy-substituted or ethoxy-substituted (said C 6-9 alkyl represents n-hexyl, n-heptyl, n-octyl, 1-methylheptyl, n-nonyl, 3-methyloctyl or 7-methyloctyl) or methoxy-substituted 6-nonenyl,
  • R 2A , R 3A , R 6A and R 7A represent hydrogen or methyl
  • R 2A forms ethylene together with R 7A , and
  • R 4A and R 5A represent hydrogen or methyl, or together represent oxo, provided that the following cases (i) - (iii) are excluded: (i) the case in which R 2A , R 3A , R 4A , R 5A , R 6A and R 7A represent hydrogen and R 1A represents n-hexyl, n-heptyl or n-nonyl, (ii) the case in which R 2A , R 3A , R 6A and R 7A represent hydrogen, R 4A and R 5A each represents methyl and R 1A represents n-hexyl, n-heptyl or n-nonyl, (iii) the case in which R 2A , R 3A , R 6A and R 7A represent methyl, R 4A and R 5A together represent oxo and R 1A represents n-nonyl.
  • R 1A represents C ⁇ -galkyl that may be optionally methoxy-substituted or ethoxy-substituted (said C 6-9 alkyl represents n-hexyl, n-heptyl, n-octyl, 1-methylheptyl, n-nonyl, 3-methyloctyl or 7-methyloctyl) or methoxy-substituted 6-nonenyl,
  • R 2A , R 3A , R 6A and R 7A represent hydrogen or methyl
  • R 2A forms ethylene together with R 7A , and
  • R 4A and R 5A represent hydrogen or methyl, or together represent oxo, provided that in case that R 4A and R 5A each represents a hydrogen atom, R 2A , R 3A , R 6A and R 7A represent hydrogen, or R 2A forms ethylene together with R 7A and R 3A and R 6A represent hydrogen, in case that R 4A and R 5A represent methyl, R 2A , R 3A , R 6A and R 7A represent hydrogen, and in case that R 4A and R 5A together represent oxo, R 2A , R 3A , R 6A and R 7A represent methyl, and further provided that, the following cases (i) - (iii) are excluded: (i) the case in which R 2A , R 3A , R 4A , R 5A , R 6A and R 7A represent hydrogen and R 1A represents n-hexyl, n-heptyl or n-nonyl, (ii) the case in which R 2A
  • R 1A represents C 6- galkyl that may be optionally methoxy-substituted or ethoxy-substituted (said C 6-9 alkyl represents n-hexyl, n-heptyl, n-octyl, 1-methylheptyl, n-nonyl, 3-methyIoctyl or 7-methyloctyl) or methoxy-substituted 6-nonenyl,
  • R 2A , R 3A , R 6A and R 7A represent methyl
  • R 4A and R 5A together represent oxo, provided that, the case, in which R 2A , R 3A , R 6A and R 7A each represents methyl, R 4A and R 5A together represent oxo and R 1A represents n-nonyl, is excluded.
  • the aforementioned preparation process (a) can be illustrated by the following reaction scheme in case that, for example, 4,4,6,6-tetramethyl-3,5-dioxo-1-cyclohex-1-enyl octanoate and, for example, 4-dimethylaminopyridine as an acid binder, are used as staring materials.
  • the compounds of the above-mentioned formula (I) can exists as tautomers as represented by the following formulae (Ia), (Ib), (Ic) and (Id). Though in the present specification they are shown with the structure of the formula (Ia) as representative, the compounds of the formula (I) include also the compounds of the formulae (Ib), (Ic) and (Id).
  • the compounds of the formula (II) used as the starting materials in the aforementioned preparation process (a) are novel compounds that have not been described yet in the existing literature. And, the compounds can be easily prepared according to the process described in, for example, Japanese Laid-open Patent Application No. 173/1990, Japanese Laid-open Patent Application No. 222/1990, Japanese Laid-open Patent Application No. 6425/1990, etc. by reacting compounds of the formula (III)
  • R 2A , R 3A , R 4A , R 5A , R 6A and R 7A have the same definition as aforementioned, with compounds of the formula (IV)
  • R 1A has the same definition as aforementioned
  • X represents halogen, preferably chlorine or bromine.
  • the compounds of the aforementioned formula (II) can be easily prepared according to the process described in, for example, WO 01/7422, etc., for example, by reacting compounds of the aforementioned formula (III) with compounds of the formula (V)
  • R 1A has the same definition as aforementioned.
  • the reaction of the above-mentioned preparation process (a) can be conducted in an appropriate diluent.
  • a diluent for example, aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, 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), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc.; ketones, for example, acetane, methyl
  • the preparation process (a) can be conducted in the presence of an acid binder.
  • an acid binder there can be mentioned, for example, as inorganic base, carbonates or bicarbonates, etc. of alkali metals or alkaline earth metals, for example, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, etc.; as organic base, tertiary amines, dialkylaminoanilines or pyridines, for example, triethylamine, 1 ,1 ,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N.N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP), 1 ,4-diazabicyclo[2,2,2]octane (DABCO), 1 ,8-diazabicyclo[5,4,0]undec-7-ene (DBU), etc.
  • TEDA triethylamine
  • DMAP 4-di
  • the preparation process (a) can be conducted in the presence of a cyanide.
  • a cyanide there can be mentioned sodium cyanide, potassium cyanide, acetone cyanohydrin, hydrogen cyanide, etc.
  • phase transfer catalyst can be used together.
  • phase transfer catalyst used in that case there can be mentioned crown ethers, for example, dibenzo-18-crown-6, dicyclohexyl-18-crown-6, 18-crown-6, etc.
  • the reaction can be conducted in the presence of a diluent.
  • a diluent used in that case there can be mentioned water; aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chlorobenzene, dichlorobenzene, etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc.; nitriles, for example, acetonitrile, propionitrile, etc.
  • the preparation process (a) can be conducted in a substantially wide range of temperature. It is preferable, however, to conduct it at the temperatures in the range of generally about 0 to about 180 0 C, particularly about 20 to about 150 ° C. Although said reaction is conducted desirably under normal pressure, it can be operated optionally under elevated pressure or under reduced pressure.
  • the aimed compounds can be obtained, for example, by reacting 1 mole of the compounds of the formula (II) in a diluent, for example, toluene, in the presence of 0.1 to 3 moles of 4-dimethylaminopyridine.
  • a diluent for example, toluene
  • the reaction temperature can be in the range of generally about -10 to about 8O 0 C, preferably about 5 to about 50 ° C.
  • said reaction is conducted desirably under normal pressure, it can be operated optionally under elevated pressure or under reduced pressure.
  • an objective compound in conducting the preparation process (a) in the presence of a cyanide, an objective compound can be obtained, for example, by reacting 1 mole of the compounds of the formula (II) in a diluent, for example, acetonitrile, in the presence of 1 to 4 moles of triethylamine and, for example, 0.01 to 1 mole of acetone cyanohydrin as a cyanide.
  • a diluent for example, acetonitrile
  • the active compounds of the aforementioned formula (I), according to the present invention show, as shown in the biological test examples described later, excellent herbicidal activities against various weeds and can be used as herbicide.
  • weeds mean, in a broader sense, all plants that grow in locations where they are not desired.
  • the compounds of the formula (I), according to the present invention act as non-selective herbicide depending upon the applied concentration.
  • the active compounds, according to the present invention can be used, for example, against the following weeds.
  • Genera of the dicotyledonous weeds Sinapis, Capsella, Leipdium, Galium, Stellaria, Chenopodium, Kochia, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Ipomoea, Polygonum, Ambrosia, Cirsi ⁇ m, Sonch ⁇ s, Solanum, Rorippa, Lamium, Veronica, Datura, Viola, Galeopsis, Papaver, Centaurea, Galinsoga, Rotala, Lindernia, Sesbania, Trifolium, Abutilon, Matricaria, Artemisia, 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, Commelina, etc.
  • Other weeds Equisetum etc.
  • the active compounds of the formula (I), according to the present invention can be used as non-selective herbicides on, for example, fields and paddies when crops are dormant, fallow land, fields and paddies before plowing, sowing, planting, or before germination after planting, footpaths between fields, farm surroundings, fields and paddies after harvest, etc., industrial terrain such as factories, rail tracks, roads, parking lots, parks, gardens, banks, playgrounds, residential land, graveyards, slopes, pastures, meadows, places with or without tree plantings, etc.
  • the active compounds of the formula (I), according to the present invention can be used for controlling undergrowth in perennial cultures, 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.
  • the active compounds of the formula (I), according to the present invention can show an even stronger herbicidal action as mixed herbicidal compositions with other herbicides, for example, the following known herbicides (generic names): sulfonylurea type herbicides: for example, chlorsulfuron, sulfometuron-methyl, chlorimuron-ethyl, triasulfuron, amidosulfuron, oxasulfuron, tribenuron-methyl, prosulfuron, ethametsulfuron-methyl, triflusulfuron-methyl, thifensulfuron-methyl, flazasulfuron, rimsulfuron, nicosulfuron, flupyrsulfuron, bensulfuron-methyl, pyrazosulfuron-ethyl, foramsulfuron, sulfosulfuron, cinosulfuron, azimsulfuron, metsulfuron-methyl, ha
  • herbicides particularly sulfometuron-methyl, phenmedipham, asulam, oxyfluorfen, simazine, atrazine, atrazine, ametryn, prometryn, triclopyr, phenoxaprop, fluazifop-butyl, 2,4-PA, MCP, isoxaben, diuron, linuron, isouron, tebuthiuron, propanil, glyphosate, bialaphos, glufosinate, amiprophos-methyl, bromoxynil, ioxynil, trifluralin, sethoxydim, imazapyr, paraquat, diquat, fentrazamide, bentazone, amitrole, carfentrazone-ethyl, pyridate, bromacil, terbacil, metribuzin, flumioxazin, azafenidin, oxadiazon, oxadia
  • the mixing ratio of the active compounds of the formula (I), according to the present invention, and other herbicides can be varied in a wide range responding to the application purposes, etc.
  • the following herbicides can be used in the following ranges: sulfonylurea type herbicides: 0.0001 to1 part by weight, preferably 0.001 to 0.1 part by weight, carbamate type herbicides: 0.001 to 10 parts by weight, preferably 0.01 to 1 part by weight, chloroacetanilide type herbicides: 0.001 to10 parts by weight, preferably 0.01 to 1 part by weight, diphenyl ether type herbicides: 0.001 to10 parts by weight, preferably 0.01to1 part by weight, triazine type herbicides: 0.001 to10 parts by weight, preferably 0.01 to1 part by weight, phenoxy acid or benzoic acid type
  • the mixed herbicidal compositions show a synergic herbicidal effect by mixing and can obtain an effect beyond expectation.
  • the active compounds of the formula (I) and mixed herbicidal compositions, according to the present invention 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 by 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. or paraffins (for example, mineral oil fractions, etc.)], alcohols (for example, butanol, glycols.
  • 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.)]
  • ketones for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
  • strongly polar solvents for example, dimethylformamide, dimethyl sulfoxide, etc.
  • organic solvents can be used as auxiliary solvents.
  • solid diluents or carriers there can be mentioned, for example, ground natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, etc.), ground synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates, etc.), etc.
  • ground natural minerals for example, kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, etc.
  • ground synthetic minerals for example, highly dispersed silicic acid, alumina, silicates, etc.
  • solid carriers for granules there can be mentioned crushed and fractionated rocks (for example, calcite, marble, pumice, sepiolite, dolomite, etc.) synthetic granules of inorganic and organic meals, particles of organic materials (for example, saw dust, coconut shells, maize cobs, tobacco stalks, etc.), etc.
  • nonionic and anionic emulsifiers for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (for example, alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates, 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 0.001 to 80 % by weight, preferably 0.01 to 70 % by weight.
  • the active compounds, of the formula (I) and the mixed herbicidal compositions, according to the present invention can be used directly as themselves or in the aforementioned formulation forms, or in application forms prepared by further dilution. They can be applied by means of, for example, watering, spraying, atomizing, granule application, etc.
  • the active compounds of the formula (I) and the mixed herbicidal compositions according to the present invention can be used at any stages before and after germination of plants.
  • the application amount of the active compounds of the formula, according to the present invention can be varied in a substantial range. It is fundamentally different depending upon the properties of effects to be desired. As the application amount, there can be mentioned in the range of generally about 0.01 to about 50kg, preferably about 0.1 to about 10kg per hectare as active compound.
  • the application amount of the mixed herbicidal compositions is different according to the kind of mixed active components, mixing ratio, mixing amount etc.
  • total mixed effective components there can be mentioned in the range of generally about 0.0001 -about 50kg, preferably about 0.001 -about 5kg per hectare.
  • a formulation of an active compound was 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
  • Table 2 Test for herbicidal effect against weeds (%)
  • Clay mineral particles (95 parts) having particle diameter distribution in the range of 0.2-2mm are put in a rotary mixer. While rotating it, the compound of the present invention No. 18 (5 parts) are sprayed together with a liquid diluent, wetted uniformly and dried at 40 to 50 0 C to obtain granules.
  • Formulation Example 3 (Emulsifiable concentrate)
  • the compound of the present invention No. 3 (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 mixed in powder to make a wettable powder.
  • Formulation Example 5 Water dispersible granule
  • the compound of the present invention No. 3 (20 parts), sodium ligninsulfonate (30 parts), bentonite (15 parts) and calcined diatomaceous earth powder (35 parts) are well mixed, added with water, extruded with 0.3mm screen and dried to obtain water dispersible granules.

Abstract

Herbicidal compositions having very quickly effective action characterized by containing compounds of the formula (I) wherein R1 represents C6 9-alkyl that may be optionally C1-4alkoxy-substituted or C6-9 alkenyl that may be optionally C1-4alkoxy-substituted, R2, R3, R6 and R7 represent hydrogen or methyl, or R2 forms ethylene together with R7, and R4 and R5 represent hydrogen or methyl, or together represent oxo, as active component.

Description

A USE OF CYCLOHEXANEDIONE DERIVATIVES AS HERBICIDE
The present invention relates to a use of cyclohexanedione derivatives as herbicide, to novel cyclohexanedione derivatives, to a process for their preparation, to novel intermediates, and to mixed herbicidal compositions.
It has been already known that some kinds of cyclohexanedione derivatives show an action as herbicide ( for example, cf U. S. Patent Specification No. 4202840 and Phytochemistry, VoU , 60 (3), p.281-288, 2002).
Further, it has been already known, too, that some kinds of cyclohexanedione derivatives show an action as insecticide and/or fungicide (for example, cf. WO 02/89587, WO 03/51806, Flavour and Fragrance Journal, VoU 5 (4), p.278-280, 2000, and Journal of Chemical Ecology, Vol. 27 (3), p.517-521 , 2001 ).
Further, in the field of organic chemistry, various kinds of cyclohexanedione derivatives have been synthesized and reported (for example, cf. U. S. Laid-open Patent Application No. 2002/4931 Specification, Synthesis, Vol.12, p.925-927, 1978, Synlett Vol.9, p.1392-1394, 2001 , YAKUGAKUZASSHI (Journal of Pharmacy, Japan), Vol.76, p.1256-1258, 1956. The known cyclohexanedione derivatives are not sufficiently satisfactory in terms of effects as herbicide, expression speed of effects and/or safety.
It has now been found that a group of cyclohexanedione derivatives of the formula (I) show excellent herbicidal activities having quickly effective action;
Figure imgf000003_0001
wherein
R1 represents Cβ-galkyl that may be optionally Ci-4alkoxy-substituted or C6-9 alkenyl that may be optionally C-i^alkoxy-substituted,
R2, R3, R6 and R7 represent hydrogen or methyl, or
R2 forms ethylene together with R7, and
R4 and R5 represent hydrogen or methyl, or together represent oxo.
The cyclohexanedione derivatives of the following formula (IA) being embraced by the aforementioned formula (I) of the present invention are novel compounds that have not been described in the existing literature yet.
The formula
Figure imgf000003_0002
wherein
R1A represents Chalky! that may be optionally C-|.4alkoxy-substituted or C6-9 alkenyl that may be optionally
Figure imgf000004_0001
R2A, R3A, R6A and R7A represent hydrogen or methyl, or
R2A forms ethylene together with R7A, and
R4A and R5A represent hydrogen or methyl, or together represent oxo, provided that the following cases (i) - (iii) are excluded: (i) the case in which R2A, R3A, R4A, R5A, R6A and R7A represent hydrogen and R1A represents n-hexyl, n-heptyl or n-nonyl, (ii) the case in which R2A, R3A, R6A and R7A represent hydrogen, R4A and R5A represent methyl and R1A represents n-hexyl, n-heptyl or n-nonyl, (iii) the case in which R2A, R3A, R6A and R7A represent methyl, R4A and R5A together represent oxo and R1A represents n-nonyl.
The compounds of the formula (IA) can be obtained by a process in which
a) compounds of the fomula (II)
Figure imgf000004_0002
wherein
R1A, R2A, R3A, R4A, R5A, R6A and R7A have the same definition as aforementioned, are reacted to a rearrangement in the presence of innert solvents, and if appropriate, in the presence of an acid binder, and if appropriate, in the presence of a cyanide, and if appropriate, in the presence of a phase-transfer catalyst. The compounds of the aforementioned formula (I) can also be prepared by the above-mentioned preparation process (a).
The cyclohexanedione derivatives of the formula (I), according to the present invention which include the novel compounds of the formula (IA) show strong herbicidal action. Though the cyclohexanedione derivatives of the formula (I) are partly and generically embraced by the general formula described in U.S. Patent Specification No. 4202840, they are not specifically described in said U.S. Patent. The cyclohexanedione derivatives of the formula (I) include the known compounds described in WO 03/51806 and Flavour and Fragrance Journal, Vol.15 (4), p.278-280, 2000, Journal of Chemical Ecology, Vol. 27 (3), p.517-521 , 2001 , Synthesis, Vol.12, p.925-927, 1978, Synlett Vol.9, p.1392-1394, 2001 , YAKUGAKUZASSHI (Journal of Pharmacy, Japan), Vol.76, p.1256-1258,1956, Khimiya Geterotsiklicheskikh Soedinenii, (3), p.329-333, 1975 and Zhunal Organicheskoi Khimii, Vol.28 (8), p.1634 - 1642, 1992, but these patent literature and non-patent literatures do not describe at all that the cyclohexanedione derivatives of the formula (I) have herbicidal effect.
The cyclohexanedione derivatives of the formula (I), according to the present invention unexpectedly show very excellent quickly effective herbicidal action, compared with the known compounds described in the above-mentioned U.S. Patent.
The cyclohexanedione derivatives of the formula (I), according to the present invention show, as specifically mentioned later, even stronger herbicidal action as mixed herbicidal compositions by mixing with other herbicidally active compounds.
In the present specification,
"Cβ-galkyl" can be straight-chain or branched-chain. There can be mentioned, for example, n-hexyl, n-heptyl, n-octyl, 1-methylheptyl, n-nonyl, 3-methyloctyl, 7-methyloctyl, etc.
As "Ce-θalkenyl" there can be mentioned, for example, 6-nonenyl, etc.
As "C-i-4alkoxy" there can be mentioned, for example, methoxy, ethoxy, etc.
In the compounds of the aforementioned formula (IA), preferably
R1A represents C6-9alkyl that may be optionally methoxy-substituted or ethoxy-substituted (said C6-9alkyl represents n-hexyl, n-heptyl, n-octyl, 1-methylheptyl, n-nonyl, 3-methyloctyl or 7-methyloctyl) or methoxy-substituted 6-nonenyl,
R2A, R3A, R6A and R7A represent hydrogen or methyl, or
R2A forms ethylene together with R7A, and
R4A and R5A represent hydrogen or methyl, or together represent oxo, provided that the following cases (i) - (iii) are excluded: (i) the case in which R2A, R3A, R4A, R5A, R6A and R7A represent hydrogen and R1A represents n-hexyl, n-heptyl or n-nonyl, (ii) the case in which R2A, R3A, R6A and R7A represent hydrogen, R4A and R5A each represents methyl and R1A represents n-hexyl, n-heptyl or n-nonyl, (iii) the case in which R2A, R3A, R6A and R7A represent methyl, R4A and R5A together represent oxo and R1A represents n-nonyl.
In the compounds of the aforementioned formula (IA), more preferably
R1A represents Cδ-galkyl that may be optionally methoxy-substituted or ethoxy-substituted (said C6-9alkyl represents n-hexyl, n-heptyl, n-octyl, 1-methylheptyl, n-nonyl, 3-methyloctyl or 7-methyloctyl) or methoxy-substituted 6-nonenyl,
R2A, R3A, R6A and R7A represent hydrogen or methyl, or
R2A forms ethylene together with R7A, and
R4A and R5A represent hydrogen or methyl, or together represent oxo, provided that in case that R4A and R5A each represents a hydrogen atom, R2A, R3A, R6A and R7A represent hydrogen, or R2A forms ethylene together with R7A and R3A and R6A represent hydrogen, in case that R4A and R5A represent methyl, R2A, R3A, R6A and R7A represent hydrogen, and in case that R4A and R5A together represent oxo, R2A, R3A, R6A and R7A represent methyl, and further provided that, the following cases (i) - (iii) are excluded: (i) the case in which R2A, R3A, R4A, R5A, R6A and R7A represent hydrogen and R1A represents n-hexyl, n-heptyl or n-nonyl, (ii) the case in which R2A, R3A, R6A and R7A represent hydrogen, R4A and R5A represent methyl and R1A represents n-hexyl, n-heptyl or n-nonyl, (iii) the case in which R2A, R3A, R6A and R7A represent methyl, R4A and R5A together represent oxo and R1A represents n-nonyl.
In the compounds of the aforementioned formula (IA), particularly preferably
R1A represents C6-galkyl that may be optionally methoxy-substituted or ethoxy-substituted (said C6-9alkyl represents n-hexyl, n-heptyl, n-octyl, 1-methylheptyl, n-nonyl, 3-methyIoctyl or 7-methyloctyl) or methoxy-substituted 6-nonenyl,
R2A, R3A, R6A and R7A represent methyl, and
R4A and R5A together represent oxo, provided that, the case, in which R2A, R3A, R6A and R7A each represents methyl, R4A and R5A together represent oxo and R1A represents n-nonyl, is excluded.
The aforementioned preparation process (a) can be illustrated by the following reaction scheme in case that, for example, 4,4,6,6-tetramethyl-3,5-dioxo-1-cyclohex-1-enyl octanoate and, for example, 4-dimethylaminopyridine as an acid binder, are used as staring materials.
Figure imgf000008_0001
The compounds of the above-mentioned formula (I) can exists as tautomers as represented by the following formulae (Ia), (Ib), (Ic) and (Id). Though in the present specification they are shown with the structure of the formula (Ia) as representative, the compounds of the formula (I) include also the compounds of the formulae (Ib), (Ic) and (Id).
Figure imgf000008_0002
Figure imgf000008_0003
Figure imgf000009_0001
The compounds of the formula (II) used as the starting materials in the aforementioned preparation process (a) are novel compounds that have not been described yet in the existing literature. And, the compounds can be easily prepared according to the process described in, for example, Japanese Laid-open Patent Application No. 173/1990, Japanese Laid-open Patent Application No. 222/1990, Japanese Laid-open Patent Application No. 6425/1990, etc. by reacting compounds of the formula (III)
Figure imgf000009_0002
wherein
R2A, R3A, R4A, R5A, R6A and R7A have the same definition as aforementioned, with compounds of the formula (IV)
Figure imgf000009_0003
wherein R1A has the same definition as aforementioned,
X represents halogen, preferably chlorine or bromine.
The compounds of the above-mentioned formula (III) are available on the market or can be prepared according to the process described in, for example, Japanese Laid-open Patent Application No. 309883/1997, European Patent No. 283162, etc.
The compounds of the above-mentioned formula (IV), a part of which are novel compounds that have not been described yet in the existing literature, can be prepared according to the process described in, for example, Journal of Organic Chemistry, Vol.59, p.2253-2256, 1994 etc.
The compounds of the aforementioned formula (II) can be easily prepared according to the process described in, for example, WO 01/7422, etc., for example, by reacting compounds of the aforementioned formula (III) with compounds of the formula (V)
Figure imgf000010_0001
wherein
R1A has the same definition as aforementioned.
The compounds of the above-mentioned formula (V), a part of which are novel compounds that have not been described yet in the existing literature, can be prepared according to the process described in, for example, Journal of Organic Chemistry, Vol.59, p.2253-2256, 1994, etc.
As specific examples of the compounds of the formula (II), used as the starting materials in the aforementioned preparation process (a), there can be mentioned as follows :
4,4,6, 6-tetramethyl-3,5-dioxo-1 -cyclohex-1 -enyl heptanoate,
4,4,6,6-tetramethyl-3,5-dioxo-1 -cyclohex-1 -enyl octanoate,
4,4,6, 6-tetramethyl-3,5-dioxo-1 -cyclohex-1 -enyl nonanoate,
4,4,6,6-tetramethyl-3,5-dioxo-1 -cyclohex-1 -enyl decanoate,
4,4,6,6-tetramethyl-3,5-dioxo-1 -cyclohex-1 -enyl 5-methoxynonanoate,
4,4,6,6-tetramethyl-3,5-dioxo-1 -cyclohex-1 -enyl 4-methoxydecanoate,
3-0X0-1 -cyclohex-1 -enyl octanoate,
3-0X0-1 -cyclohex-1 -enyl nonanoate,
5,5-dimethyl-3-oxo-1 -cyclohex-1 -enyl octanoate,
5,5-dimethyl-3-oxo-1 -cyclohex-1 -enyl nonanoate,
4-oxo-bicyclo[3.2.1]oct-2-en-2-yl octanoate,
4-oxo-bicyclo[3.2.1]oct-2-en-2-yl nonanoate, and so on.
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, cyclohexane, 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), tetrahydrofuran (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, 1 ,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA), 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 binder. As said acid binder there can be mentioned, for example, as inorganic base, carbonates or bicarbonates, etc. of alkali metals or alkaline earth metals, for example, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, etc.; as organic base, tertiary amines, dialkylaminoanilines or pyridines, for example, triethylamine, 1 ,1 ,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N.N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP), 1 ,4-diazabicyclo[2,2,2]octane (DABCO), 1 ,8-diazabicyclo[5,4,0]undec-7-ene (DBU), etc.
The preparation process (a) can be conducted in the presence of a cyanide. As examples of said cyanide there can be mentioned sodium cyanide, potassium cyanide, acetone cyanohydrin, hydrogen cyanide, etc.
In case that the above-mentioned preparation process (a) is conducted in the presence of a cyanide, a phase transfer catalyst can be used together. As examples of said phase transfer catalyst used in that case there can be mentioned crown ethers, for example, dibenzo-18-crown-6, dicyclohexyl-18-crown-6, 18-crown-6, etc.
In case of using a phase transfer catalyst, the reaction can be conducted in the presence of a diluent. As examples of the diluent used in that case there can be mentioned water; aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chlorobenzene, dichlorobenzene, etc.; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc.; nitriles, for example, acetonitrile, propionitrile, etc.
The preparation process (a) can be conducted in a substantially wide range of temperature. It is preferable, however, to conduct it at the temperatures in the range of generally about 0 to about 1800C, particularly about 20 to about 150°C. Although said reaction is conducted desirably under normal pressure, it can be operated optionally under elevated pressure or under reduced pressure.
In conducting the preparation process (a), the aimed compounds can be obtained, for example, by reacting 1 mole of the compounds of the formula (II) in a diluent, for example, toluene, in the presence of 0.1 to 3 moles of 4-dimethylaminopyridine.
In case of conducting the preparation process (a) in the presence of a cyanide, the reaction temperature can be in the range of generally about -10 to about 8O0C, preferably about 5 to about 50°C. Although said reaction is conducted desirably under normal pressure, it can be operated optionally under elevated pressure or under reduced pressure.
In conducting the preparation process (a) in the presence of a cyanide, an objective compound can be obtained, for example, by reacting 1 mole of the compounds of the formula (II) in a diluent, for example, acetonitrile, in the presence of 1 to 4 moles of triethylamine and, for example, 0.01 to 1 mole of acetone cyanohydrin as a cyanide.
The active compounds of the aforementioned formula (I), according to the present invention, show, as shown in the biological test examples described later, excellent herbicidal activities against various weeds and can be used as herbicide. 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 formula (I), according to the present invention, act as non-selective herbicide depending upon the applied concentration. The active compounds, according to the present invention, can be used, for example, against the following weeds.
Genera of the dicotyledonous weeds: Sinapis, Capsella, Leipdium, Galium, Stellaria, Chenopodium, Kochia, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Ipomoea, Polygonum, Ambrosia, Cirsiυm, Sonchυs, Solanum, Rorippa, Lamium, Veronica, Datura, Viola, Galeopsis, Papaver, Centaurea, Galinsoga, Rotala, Lindernia, Sesbania, Trifolium, Abutilon, Matricaria, Artemisia, 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, Commelina, etc. Other weeds: Equisetum etc.
- The active compounds of the formula (I), according to the present invention, can be used as non-selective herbicides on, for example, fields and paddies when crops are dormant, fallow land, fields and paddies before plowing, sowing, planting, or before germination after planting, footpaths between fields, farm surroundings, fields and paddies after harvest, etc., industrial terrain such as factories, rail tracks, roads, parking lots, parks, gardens, banks, playgrounds, residential land, graveyards, slopes, pastures, meadows, places with or without tree plantings, etc.
Moreover, the active compounds of the formula (I), according to the present invention, can be used for controlling undergrowth in perennial cultures, 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.
The active compounds of the formula (I), according to the present invention, can show an even stronger herbicidal action as mixed herbicidal compositions with other herbicides, for example, the following known herbicides (generic names): sulfonylurea type herbicides: for example, chlorsulfuron, sulfometuron-methyl, chlorimuron-ethyl, triasulfuron, amidosulfuron, oxasulfuron, tribenuron-methyl, prosulfuron, ethametsulfuron-methyl, triflusulfuron-methyl, thifensulfuron-methyl, flazasulfuron, rimsulfuron, nicosulfuron, flupyrsulfuron, bensulfuron-methyl, pyrazosulfuron-ethyl, foramsulfuron, sulfosulfuron, cinosulfuron, azimsulfuron, metsulfuron-methyl, halosulfuron-methyl, ethoxysulfuron, cyclosulfamuron, iodosulfuron, etc.; carbamate type herbicides: for example, phenmedipham, chlorpropham, asulam, benthiocarb, molinate, esprocarb, pyributycarb, dimepiperate, swep (MCC), etc.; chloroacetanilide type herbicides: for example, propachlor, metazachlor, alachlor, acetochlor, metolachlor, butachlor, pretilachlor, thenylchlor, etc.; diphenyl ether type herbicides: for example, acifluorfen, oxyfluorfen, lactofen, fomesafen, aclonifen, chlormethoxyfen, bifenox, CNP, etc.; triazine type herbicides: for example, simazine, atrazine, propazine, cyanazine, ametryn, simetryn, dimethametryn, prometryne etc.; phenoxy acid or benzoic acid type herbicides: for example, 2,3,6-TBA, dicamba, quinclorac, quinmerac, clopyralid, picloram, triclopyr, fluroxypyr, phenoxaprop, diclofop-methyl, fluazifop-methyl, haloxyfop-methyl, quizalofop-ethyl, cyhalofop-butyl, 2,4-PA, MCP, MCPB, phenothiol, etc.; acid amide or urea type herbicides: for example, isoxaben, diflufenican, diuron, linuron, fiuometuron, difenoxuron, methyldymron, isoproturon, isouron, tebuthiuron, methabenzthiazuron, propanil, mefenacet, clomeprop, naproanilide, bromobutide, dymron, cumyluron, etobenzanid, oxaziclomefone, etc.; organophosphorous herbicides: for example, glyphosate, bialaphos, glufosinate, amiprophos-methyl, anilofos, bensulide, piperophos, butamifos, etc.; dinitroaniline type herbicides: for example, bromoxynil, ioxynil, dinoseb, trifluralin, prodiamine, etc.; cyclohexanedione type herbicides: for example, alloxydim, sethoxydim, cloproxydim, cresodim, cycloxydim, tralkoxydim, etc.; imidazolinone type herbicides: for example, imazamethabenz, imazapyr, imazamethapyr, imazethapyr, imazamox, imazaquin, etc.; bipyridium type herbicides: for example, paraquat, diquat, etc.; carbamoyltetrazolinone type herbicides: for example, fentrazamide etc.; other herbicides: for example, bentazone, tridiphane, indanofan, amitrole, carfentrazone-ethyl, sulfentrazone, fenchlorazole-ethyl, isoxaflutole, clomazone, maleic hydrazide, pyridate, chloridazon, norflurazon, pyrithiobac, bromacil, terbacil, metribuzin, oxaziclomefone, cinmethylin, flumiclorac-pentyl, flumioxazin, fluthiacet-methyl, azafenidin, benfuresate, oxadiazon, oxadiargyl, pentoxazone, cafenstrole, pyrimenobac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyraflufen-ethyl, benzobicyclon, dithiopyr, dalapon, chlorthiamid etc.
Among the above-mentioned herbicides, particularly sulfometuron-methyl, phenmedipham, asulam, oxyfluorfen, simazine, atrazine, atrazine, ametryn, prometryn, triclopyr, phenoxaprop, fluazifop-butyl, 2,4-PA, MCP, isoxaben, diuron, linuron, isouron, tebuthiuron, propanil, glyphosate, bialaphos, glufosinate, amiprophos-methyl, bromoxynil, ioxynil, trifluralin, sethoxydim, imazapyr, paraquat, diquat, fentrazamide, bentazone, amitrole, carfentrazone-ethyl, pyridate, bromacil, terbacil, metribuzin, flumioxazin, azafenidin, oxadiazon, oxadiargyl, bispyribac-sodium and pyraflufen-ethyl are preferable.
The above-mentioned active compounds are known herbicides described in "Pesticide Manual" published in 2000 by British Crop Protect Council.
In the mixed herbicidal compositions, according to the present invention, the mixing ratio of the active compounds of the formula (I), according to the present invention, and other herbicides can be varied in a wide range responding to the application purposes, etc. For example, to 1 part by weight of a compound of the formula (I), according to the present invention, the following herbicides can be used in the following ranges: sulfonylurea type herbicides: 0.0001 to1 part by weight, preferably 0.001 to 0.1 part by weight, carbamate type herbicides: 0.001 to 10 parts by weight, preferably 0.01 to 1 part by weight, chloroacetanilide type herbicides: 0.001 to10 parts by weight, preferably 0.01 to 1 part by weight, diphenyl ether type herbicides: 0.001 to10 parts by weight, preferably 0.01to1 part by weight, triazine type herbicides: 0.001 to10 parts by weight, preferably 0.01 to1 part by weight, phenoxy acid or benzoic acid type herbicides: 0.0001 to10 part by weight, preferably 0.001 to1 part by weight, acid amide or urea type herbicides: 0.001 to 10 parts by weight, preferably 0.01 to1 part by weight, organophosphorous herbicides: 0.001 to 10 parts by weight, preferably 0.01 to 1 part by weight, dinitroaniline type herbicides: 0.001 to 10 parts by weight, preferably 0.01 to 1 part by weight, cyclohexanedione type herbicides: 0.001 to10 parts by weight, preferably 0.01 to1 part by weight, imidazolinone type herbicides: 0.0001 to1 part by weight, preferably 0.001 to 0.1 part by weight, bipyridium type herbicides: 0.001 to 10 parts by weight, preferably 0.01 to 1 part by weight, carbamoyltetrazolinone type herbicides: 0.001 to 1 part by weight, preferably 0.01 to
1 part by weight, as other herbicides: for example, bentazone: 0.001 to 10 parts by weight, preferably 0.1 to 2 parts by weight, amitrole: 0.001 to10 parts by weight, preferably 0.01 to 1 part by weight, carfentrazone-ethyl: 0.001 to10 parts by weight, preferably 0.005 to 0.1 part by weight, pyridate: 0.01 to10 parts by weight, preferably 0.1 to1 part by weight, bromacil: 0.001 to10 parts by weight, preferably 0.1 to 2 parts by weight, terbacil: 0.001 to10 parts by weight, preferably 0.1 to 2 parts by weight, metribuzin: 0.001 to10 parts by weight, preferably 0.01 to1 part by weight, flumioxazin: 0.001-1 part by weight, preferably 0.01 to 1 part by weight, azafenidin: 0.001 to10 parts by weight, preferably 0.01 to 1 part by weight, oxadiazon: 0.001 to 10 parts by weight, preferably 0.01 to1 part by weight, oxadiargyl: 0.001 to10 parts by weight, preferably 0.01 to1 part by weight, bispyribac-sodium: 0.001 to10 parts by weight, preferably 0.01 to 1 part by weight, pyrafluf en-ethyl: 0.0001 to1 parts by weight, preferably 0.001 to 0.5 parts by weight.
The mixed herbicidal compositions, according to the present invention, show a synergic herbicidal effect by mixing and can obtain an effect beyond expectation.
The active compounds of the formula (I) and mixed herbicidal compositions, according to the present invention, 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 by 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. When water is used as extender, for example, organic solvents can be used as auxiliary solvents. As solid diluents or carriers there can be mentioned, for example, ground natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, etc.), ground synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates, etc.), etc. As solid carriers for granules there can be mentioned crushed and fractionated rocks (for example, calcite, marble, pumice, sepiolite, dolomite, etc.) synthetic granules of inorganic and organic meals, particles of organic materials (for example, saw dust, coconut shells, maize cobs, tobacco stalks, etc.), 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, arylsulfonates, 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 0.001 to 80 % by weight, preferably 0.01 to 70 % by weight.
The active compounds, of the formula (I) and the mixed herbicidal compositions, according to the present invention, can be used directly as themselves or in the aforementioned formulation forms, or in application forms prepared by further dilution. They can be applied by means of, for example, watering, spraying, atomizing, granule application, etc.
The active compounds of the formula (I) and the mixed herbicidal compositions according to the present invention, can be used at any stages before and after germination of plants.
The application amount of the active compounds of the formula, according to the present invention, can be varied in a substantial range. It is fundamentally different depending upon the properties of effects to be desired. As the application amount, there can be mentioned in the range of generally about 0.01 to about 50kg, preferably about 0.1 to about 10kg per hectare as active compound.
The application amount of the mixed herbicidal compositions is different according to the kind of mixed active components, mixing ratio, mixing amount etc. As total mixed effective components there can be mentioned in the range of generally about 0.0001 -about 50kg, preferably about 0.001 -about 5kg per hectare.
Then the preparation and application of the compounds of 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 imgf000022_0001
4,4,6,6-Tetramethyl-3,5-dioxo-1-cyclohex-1-enyl octanoate (1.48g) was dissolved in acetonitrile (20ml) and triethylamine (0.97g) and acetone cyanohydrin (0.04g) were added thereto. The mixture was stirred at room temperature for 5 hours. After distilling off the solvent, the reaction mixture was acidified through addition of diluted hydrochloric acid and extracted with ethyl acetate (150ml). The organic layer was 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 (ethyl acetate: hexane =1 :3) to obtain the objective δ-hydroxy^^.θ.θ-tetramethyM-octanoyl-cyclohex^-ene-i ,3-dione (0.51 g). nD 20 1.4937 Synthesis Example 2
Figure imgf000022_0002
4,4,6,6-Tetramethyl-3,5-dioxo-1-cyclohex-1-enyl nonanoate (0.64g) was dissolved in toluene (5ml) and 4-dimethylaminopyridine (0.05g) was added thereto. The mixture was stirred for 2 hours under reflux. After distilling off the solvent, the reaction mixture was acidified through addition of diluted hydrochloric acid and extracted with ethyl acetate (100ml). The organic layer was 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 (ethyl acetate: hexane =1 :3) to obtain the objective δ-hydroxy^^.θ.θ-tetramethyl^-nonanoyl-cyclohex^-ene-I .S-dione (0.42g). nD 20 1.4932
Examples of the cyclohexanedione derivatives of the aforementioned formula
(I), which include the compounds of the formula (IA) and also include known compounds, easily obtained by same manner to the above-mentioned Synthesis Examples 1 or 2, or according to the general process of the aforementioned preparation process (a), are shown, together with the compounds of the above-mentioned Synthesis Examples land 2, in the following Table 1.
In Table 1 , in relation to the part of the following formula (Qn) of the compounds of the formula (I) of the present invention:
Figure imgf000023_0001
Q1 represents the group
Figure imgf000023_0002
Q2 represents the group
Figure imgf000024_0001
Q3 represents the group
Figure imgf000024_0002
Q4 represents the group
Figure imgf000024_0003
Table 1
Figure imgf000025_0001
Figure imgf000025_0003
Reference Example 1 (Preparation of intermediate)
Figure imgf000025_0002
To a solution of 2,2,4,4-Tetramethylcyclohexane-1 ,3,5-trione (0.8Og) in THF (20ml), triethylamine (0.6Og) was added and the solution was stirred at 1O0C for 30 minutes. A solution of n-octanoyl chloride (0.94g) in THF (5ml) was added thereto dropwise at 50C and the solution was stirred at room temperature for 3 hours. After the reaction, the reaction solution was diluted with cold water and extracted with ethyl acetate (100ml). The organic layer was washed with diluted hydrochloric acid and then with an aqueous solution of sodium hydrogen carbonate, and dried over anhydrous magnesium sulfate. The residue, obtained by distilling off ethyl acetate, was purified by silica gel column chromatography (ethyl acetate: hexane =1 :3) to obtain the objective 4,4,6,6-tetramethyl-3,5-dioxo-1-cyclohex-1-enyl octanoate (1.48g). nD 20 1.4735
Biological Test Example 1 : Test for herbicidal effect against 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 compound was 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 green house, on the surface layer of a 120 cm3 pot filled with field soil, seeds of foxtail and common amaranth were sown and covered with soil. After 10 days (weeds were at 2-leaf stage in average) a prescribed, diluted solution of the formulation of each active compound was uniformly sprayed on foliage part of plant in each test pot. Five days after the spraying the degree of herbicidal effect was examined. The herbicidal effect was rated as 100% in the case of complete death and as 0% in the case of no herbicidal effect.
As specific examples, the results with the compounds of the compound no. 1 , 2, 3, 4, 6, 8 and 10 are shown in Table 2. Table 2: Test for herbicidal effect against weeds (%)
Figure imgf000027_0001
Biological Test Example 2: Test for synergistic effect of foliage spraying of herbicidal compositions
In a green house, on the surface layer of a 120 cm3 pot filled with field soil, seeds of barnyard grass, foxtail, common amaranth and knotweed were sown and covered with soil. After 10 days (weeds were at 2-leaf stage in average) each active compound and each active compound mixture, prepared in the same manner as the above-mentioned Test Example 1 were uniformly sprayed on foliage part of plant in each test pot. Three days after the spraying the degree of herbicidal effect was examined. The herbicidal effect was rated as 100% in the case of complete death and as 0% in the case of no herbicidal effect.
As specific examples, the results of the cases, in which the compound of the compound number 3 as a compound of the present invention and glufosinate as a known herbicide were used, are shown in Table 3.
Table 3: Test for synergistic effect of foliage spraying of herbicidal compositions
Figure imgf000028_0001
Formulation Example 1 (Granule)
To a mixture of the compound of the present invention No. 18 (10 parts), bentonite (montmorillonite) (30 parts), talc (58 parts) and ligninsulfonate salt (2 parts), water (25 parts) was added, well kneaded, made into granules of 10 to 40 mesh by an extrusion granulator and dried at 40 to 5O0C to obtain granules. Formulation Example 2 (Granules)
Clay mineral particles (95 parts) having particle diameter distribution in the range of 0.2-2mm are put in a rotary mixer. While rotating it, the compound of the present invention No. 18 (5 parts) are sprayed together with a liquid diluent, wetted uniformly and dried at 40 to 500C to obtain granules. Formulation Example 3 (Emulsifiable concentrate)
The compound of the present invention No. 3 (30 parts), xylene (55 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. 3 (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 mixed in powder to make a wettable powder. Formulation Example 5 (Water dispersible granule)
The compound of the present invention No. 3 (20 parts), sodium ligninsulfonate (30 parts), bentonite (15 parts) and calcined diatomaceous earth powder (35 parts) are well mixed, added with water, extruded with 0.3mm screen and dried to obtain water dispersible granules.

Claims

Claims
1 ) Herbicidal compositions having very quickly effective action characterized by containing compounds of the formula
Figure imgf000030_0001
wherein
R1 represents C6-9alkyl that may be optionally Ci-4alkoxy-substituted or Cδ-g alkenyl that may be optionally C-ι-4alkoxy-substituted,
R2, R3, R6 and R7 represent hydrogen or methyl, or
R2 forms ethylene together with R7, and
R4 and R5 represent hydrogen or methyl, or together represent oxo, as active component.
2) Novel cyclohexanedione derivatives of the formula
( IA )
Figure imgf000030_0002
wherein
R1A represents C-6-galkyl that may be optionally C1.4alkoxy-substitut.ed or Cβ-g alkenyl that may be optionally Ci.4alkoxy-substituted,
R2A, R3A, R6A and R7A represent hydrogen or methyl, or
R2A forms ethylene together with R7A, and
R4A and R5A represent hydrogen or methyl, or together represent oxo, provided that the following cases (i) - (iii) are excluded: (i) the case in which R2A, R3A, R4A, R5A, R6A and R7A represent hydrogen and R1A represents n-hexyl, n-heptyl or n-nonyl, (ii) the case in which R2A, R3A, R6A and R7A represent hydrogen, R4A and R5A represent methyl and R1A represents n-hexyl, n-heptyl or n-nonyl, (iii) the case in which R2A, R3A, R6A and R7A represent methyl, R4A and R5A together represent oxo and R1A represents n-nonyl. 3) The compounds set forth in Claim 2 wherein
R1A represents C-6-galkyl that may be optionally methoxy-substituted or ethoxy-substituted (said C-6-galkyl represents n-hexyl, n-heptyl, n-octyl, 1-methylheptyl, n-nonyl, 3-methyloctyl or 7-methyloctyl) or methoxy-substituted 6-nonenyl,
R2*, R3A, R6A and R7A represent hydrogen or methyl, or
R2A forms ethylene together with R7A, and
R4A and R5A represent hydrogen or methyl, or together represent oxo, provided that, the following cases (i) - (iii) are excluded: (i) the case in which R2A, R3A, R4A, R5A, R6A and R7A represent hydrogen and R1A represents n-hexyl, n-heptyl or n-nonyl, (ii) the case in which R2A, R3A, R6A and R7A represent hydrogen, R4A and R5A represent methyl and R1A represents n-hexyl, n-heptyl or n-nonyl, the case in which R2A, R3A, R6A and R7A represent methyl, R4A and R5A together represent oxo and R1A represents n-nonyl.
4) The compounds set forth in Claim 2 wherein
R1A represents C6-9alkyl that may be optionally methoxy-substituted or ethoxy-substituted (said C-6-galkyl represents n-hexyl, n-heptyl, n-octyl, 1-methylheptyl, n-nonyl, 3-methyloctyl or 7-methyloctyl) or methoxy-substituted 6-nonenyl,
R2A, R3A, R6A and R7A represent hydrogen or methyl, or
R2A forms ethylene together with R7A, and
R4A and R5A represent hydrogen or methyl, or together represent oxo, provided that, in case that R4A and R5A represent hydrogen, R2A, R3A, R6A and R7A represent hydrogen, or R2A forms ethylene together with R7A, and R3A and R6A each represent hydrogen, in case that R4A and R5A represent methyl, R2A, R3A, R6A and R7A represent hydrogen, and in case that R4A and R5A together represent oxo, R2A, R3A, R6A and R7A represent methyl, and further provided that the following cases (i) - (iii) are excluded: (i) the case in which R2A, R3A, R4A, R5A, R6A and R7A represent hydrogen and R1A represents n-hexyl, n-heptyl or n-nonyl, (ii) the case in which R2*, R3A, R6A and R7A represent hydrogen, R4A and R i£5A
represent methyl and R1A represents n-hexyl, n-heptyl or n-nonyl, (iii) the case in which R2A, R3A, R6A and R7A represent methyl, R4A and R5A together represent oxo and R1A represents n-nonyl.
5) The compounds set forth in Claim 2 wherein R1A represents C6-galkyl that may be optionally methoxy-substituted or ethoxy-substituted (said C6-9alkyl represents n-hexyl, n-heptyl, n-octyl, 1-methylheptyl, n-nonyl, 3-methyloctyl or 7-methyloctyl) or methoxy-substituted 6-nonenyl,
R2A, R3A, R6A and R7A represent methyl, and
R4A and R5A together represent oxo, provided that the case, in which R2A, R3A, R6A and R7A represent methyl, R4A and R5A together represent oxo and R1A represents n-nonyl, is excluded. 6) A process for the preparations of the compounds of the formula (IA)
Figure imgf000033_0001
wherein
R1A represents Chalky! that may be optionally C1-4alkoxy-substituted or Cβ-g alkenyl that may be optionally C1-4alkoxy-substituted,
R2A, R3A, R6A and R7A represent hydrogen or methyl, or
R2A forms ethylene together with R7A, and
R4A and R5A represent hydrogen or methyl, or together represent oxo, provided that the following cases (i) - (iii) are excluded: (i) the case in which R2A, R3A,_R4A, R5A, R6A and R7A represent hydrogen and R1A represents n-hexyl, n-heptyl or n-nonyl, (ii) the case in which R2A, R3A, R6A and R7A represent hydrogen, R4A and R5A represents methyl and R1A represents n-hexyl, n-heptyl or n-nonyl, (iii) the case in which R2A, R3A, R6A and R7A represent methyl, R4A and R5A together represent oxo and R1A represents n-nonyl characterized in that compounds of the fomula (II)
Figure imgf000034_0001
wherein
R1A, R2A, R3A, R4A, R5A, R6A and R7A have the same definition as aforementioned, are reacted to a rearrangement in the presence of innert solvents, and if appropriate, in the presence of an acid binder, and if appropriate, in the presence of a cyanide, and if appropriate, in the presence of a phase-transfer catalyst. 7) Mixed herbicide compositions characterized by containing (a) a compound of the formula (I) set forth in Claim 1 and (b)-at least one kind of other herbicide selected from the group consisting of sulfonylurea type herbicides, carbamate type herbicides, chloroacetanilide type herbicides, diphenyl ether triazine type herbicides, phenoxy acid or benzoic acid type herbicides, acid amide or urea type herbicides, organophosphorous herbicides, -dinitroaniline type herbicides, cyclohexanedione type herbicides, imidazolinone type •-- herbicides, bipyridium type herbicides, carbamoyltetrazolinone type herbicides, bentazone, tridiphane, indanofan, amitrole, carfentrazone-ethyl, sulfentrazone, fenchlorazole-ethyl, isoxaflutole, clomazone, maleic hydrazide, pyridate, chloridazon, norflurazon, pyrithiobac, bromacil, terbacil, metribuzin, oxaziclomefone, cinmethylin, flumiclorac-pentyl, flumioxazin, fluthiacet-methyl, azafθnidin, benfuresate, oxadiazon, oxadiargyl, pentoxazone, cafenstrolθ, pyrimenobac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyraflufen-ethyl, benzobicyclon, dithiopyr, dalapon and chlorthiamid, as active components.
8) Process for combating weeds, characterized in that cyclohexanedione derivatives of the formula (I) according to claim 1 are allowed to act on weeds and / or their habitat.
9) Use of cyclohexanedione derivatives of the formula (I) according to claim 1 for combating weeds.
10) Process for the preparation of herbicidal compositions, characterized in that cyclohexanedione derivatives of the formula (I) according to claim 1 are mixed with extends and / or surface active agents.
11 ) Compounds of the formula
Figure imgf000035_0001
wherein
R1A represents C6-galkyl that may be optionally C-i^alkoxy-substituted or C6-9 alkenyl that may be optionally Ci-4alkoxy-substituted,
R2A, R3A, R6A and R7A represent hydrogen or methyl, or R2A forms ethylene together with R7A, and R4A and R5A represent hydrogen or methyl, or together represent oxo, provided that the following cases (i) - (iii) are excluded:
(i) the case in which R2A, R3A, R4A, R5A, R6A and R7A represent hydrogen and R1A represents n-hexyl, n-heptyl or n-nonyl,
(ii) the case in which R2A, R3A, R6A and R7A represent hydrogen, R4A and R5A represent methyl and R1A represents n-hexyl, n-heptyl or n-nonyl, (iii) the case in which R2A, R3A, R6A and R7A represent methyl, R4A and R5A together represent oxo and R1A represents n-nonyl.
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