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WO1997019071A1 - Derives de 2-cyano-1,3-dione, leur preparation et leur utilisation comme herbicides - Google Patents

Derives de 2-cyano-1,3-dione, leur preparation et leur utilisation comme herbicides Download PDF

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WO1997019071A1
WO1997019071A1 PCT/EP1996/005065 EP9605065W WO9719071A1 WO 1997019071 A1 WO1997019071 A1 WO 1997019071A1 EP 9605065 W EP9605065 W EP 9605065W WO 9719071 A1 WO9719071 A1 WO 9719071A1
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alkyl
alkoxy
haloalkyl
haloalkoxy
nitro
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PCT/EP1996/005065
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German (de)
English (en)
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Martina Otten
Wolfgang Von Deyn
Stefan Engel
Regina Luise Hill
Uwe Kardorff
Marcus Vossen
Peter Plath
Helmut Walter
Karl-Otto Westphalen
Ulf Misslitz
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Basf Aktiengesellschaft
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Priority to AU76269/96A priority Critical patent/AU7626996A/en
Publication of WO1997019071A1 publication Critical patent/WO1997019071A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D275/06—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to the ring sulfur atom
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/18—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with sulfur as the ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes 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 carbon atoms of the hetero ring
    • C07D333/64—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes 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 carbon atoms of the hetero ring
    • C07D333/66—Nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans

Definitions

  • the present invention relates to novel phenyldiketone derivatives with herbicidal activity, processes for the preparation of the phenyldiketone derivatives, agents which contain them and the use of these derivatives or agents containing them for grass weeding /
  • Herbicidal phenyldiketone derivatives are known from the literature, for example from EP 625505. However, the herbicidal properties of the known compounds and the compatibility with crop plants can only give satisfactory results to a limited extent.
  • the task was to find new phenyldiketone derivatives with improved properties.
  • L, M is hydrogen, C 1 -C 3 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl,
  • CR 10 R 11 CR 7 -SR 8 ; 1,3-dioxanyl or 1,3-dioxolanyl substituted with hydrogen or C 1 -C 4 alkyl; a heteroatom selected from the group consisting of oxygen, sulfur and nitrogen;
  • R 1 C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or NR 14 ;
  • R 2 is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or NR 14 ;
  • R 3 is hydrogen, -NR 9 R 4 ; C 1 -C 6 alkyl, C 1 -C 6 haloalkyl,
  • R 4 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl,
  • R 3 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl,
  • R 7 is hydrogen, C 1 -C 6 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl,
  • C 1 -C 4 haloalkoxy optionally substituted phenyl, where the substituents can consist of one to three halogens, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, nitro; R 7 and R 21 or R 7 and R 23 or R 7 and R 12 can form a bond; R 8 is hydrogen, C 1 -C 6 alkyl, C 1 -C 4 haloalkyl, substituted phenyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 - Haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro; substituted benzyl where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloal
  • R 10 , R 11 independently of one another are hydrogen, C 1 -C 6 alkyl; Phenyl optionally substituted with one to three halogens, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, nitro;
  • R 10 and R 12 or R 10 and R 23 or R 10 and R 21 may form a bond;
  • R 12 , R 13 independently of one another are hydrogen, C 1 -C 6 alkyl,
  • C 1 -C 6 haloalkyl C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy; optionally substituted phenyl where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
  • R 14 C 1 -C 4 alkyl
  • R 21 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy,
  • C 1 -C 6 haloalkoxy optionally substituted phenyl where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
  • R 22 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy,
  • C 1 -C 6 haloalkoxy optionally substituted phenyl where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
  • R 23 is hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy;
  • phenyl or benzyl optionally substituted with C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
  • phenyldiketone derivatives can exist in the following tautomeric forms:
  • L, M, X, Y, n and R 15 have the meaning given at the outset and T stands for halogen.
  • the first step of the reaction sequence is such that magnesium and a small amount of CCl 4 are added to a methanolic solution of a cyanoketone of the formula AI and this is allowed to react to the magnesium enolate.
  • Analog C-acylations of cyanoketones are described, for example, in EP-A 496 630 and EP-A 496 631.
  • the magnesium enolate of the formula A2 obtained is dissolved in toluene or acetonitrile, with acetonitrile being preferred, and the amount of the acid chloride of the formula III equivalent to AI is then added dropwise as an acetonitrile solution.
  • the reaction is complete.
  • the mixture is concentrated in vacuo, the remaining residue is taken up in a solvent such as ethyl acetate or methylene chloride and 10%.
  • HCl washed to break down the magnesium salt.
  • the product is precipitated from the remaining residue by rubbing with a hydrocarbon such as petroleum ether, cyclohexane or n-pentane.
  • the cyanoketones of the formula AI used as starting materials are generally known compounds. They can be obtained, for example, by reacting cyanoacetic acid with butyllithium and then with an acid chloride R 15 -COCl.
  • the acid chlorides R 15 -COCl are obtained in a manner known per se from the corresponding carboxylic acids R 15 -COOH by reaction with thionyl chloride.
  • the carboxylic acids R 15 -COOH are compounds known from the literature: pivalic acid and cyclopropanecarboxylic acid are commercial compounds.
  • DMethylcyclopropanecarboxylic acid is either obtained by saponification from the commercially available ethyl ester or obtained in a known manner by methylation of the lithium ⁇ -lithiocylopropanecarboxylate [Warner + Le, JOC 47, 893 (1982)].
  • 1-methylthiocyclopropanecarboxylic acid is obtained in a known manner from the 1-methylthiocyclopropanecarboxylic acid nitrile, which in turn can be prepared from methylmercaptoacetonitrile and ethylene dibromide in the presence of sodium amide
  • AlCl 3 or SnCl 4 are preferred as Lewis acids and polyphosphoric acid and sulfuric acid are preferred as protonic acids according to Can. J. Chem. 1981, 59, 199; Chem. Ber. 1925, 58, 1625; Chem. Ber. 1926, 59, 1074; Phosp. and sulf. 1984, 19, 31.
  • Thiochromenonic acids can continue to be e.g. Elimination of hydrogen halide from 3-halothiochromanonic acids or e.g. by reacting the substituted thiophenolic acids with substituted ⁇ -alkylacetoacetic esters in the presence of phosphorus pentoxide according to Ann. Chem. 1964, 680, 40.
  • the arylthio compounds IV can be obtained, for example, by a Sandmeyer reaction from corresponding anilines, which in turn are synthesized by reducing suitable nitro compounds in accordance with Organikum 19th edition 1992, 552ff.
  • the reactants and the base are expediently used in equimolar amounts.
  • the reaction mixture is preferably stirred at 20-100 ° C., in particular at 20-40 ° C.
  • Working up is carried out, for example, by pouring the reaction mixture onto water, acidifying the aqueous phase with mineral acids such as hydrochloric acid or sulfuric acid and suctioning off the product of value or by extraction with methylene chloride or Extracted ethyl acetate, dried and freed from the solvent.
  • the ester can be reacted without further purification.
  • the thiochromenone ester can be reacted, for example, by reacting an arylthio compound with an acetylenecarboxylic acid derivative in water or solvent at a temperature of 0-140 ° Implement C.
  • Working up is carried out in a manner known per se by adding water and dilute mineral acid such as hydrochloric acid. The product of value is either suctioned off or by extraction with methylene chloride or ethyl acetate, followed by
  • the intermediates of formula III can be obtained by reactions known from the literature, such as reduction according to Jerry March "Advanced Organic Chemistry, Fourth Ed., E.g. S.910ff, oximation according to Jerry March” Advanced Organic Chemistry, Fourth Ed., E.g. P.934, 935, 1039, 1226, 405ff, conversion into imines and amines according to Jerry March "Advanced Organic Chemistry, Fourth Ed., Ketalization, alkylation, halogenation, elimination and oxidation according to Jerry March” Advanced Organic Chemistry, Fourth Ed. be further functionalized.
  • 3-alkoxy-1,2-benzisothiazoles can be obtained starting from corresponding saccharin derivatives or 1,2-benzisothiazoles by, for example, reaction with PCl 5 , POCI 3 or chlorine and alcohol, optionally in the presence of an auxiliary base such as, for example, triethylamine, which is described, for example, in US 4,571,429, Arch. Pharm. 1984, 317, 807, US 4461901, US 450916, J. Med. Chem. 1986, 29, 359.
  • Saccharin carboxylic acids can be described by literature methods according to Ann. Chem. 427, 231, 1922, Chem. Ber. 13, 1554, 1980, Chem. Ber. 25, 1740, 1892, DE-OS 3607343, German patent application P 44 27 995.7 can be obtained.
  • the benzoic acids of formula III can also be obtained by the corresponding bromo or iodo substituted compound of formula VII
  • Y, L, M, X and n have the meaning described above, in the presence of a palladium, nickel, cobalt or rhodium transition metal catalyst and a base with carbon monoxide and water under elevated pressure.
  • Palladium can be metallic or in the form of customary salts such as in the form of halogen compounds, for example PdCl 2 , RhCl 3 -H 2 O, acetates, for example Pd (OAc) 2 , cyanides etc. in the known valence levels.
  • phosphine ligand is widely variable. For example, they can be represented by the following formulas: or
  • n 1, 2, 3 or 4 and the radicals R 24 to R 26 are low molecular weight alkyl, for example C 1 -C 6 alkyl, aryl, C 1 -C 4 alkylaryl, for example benzyl, phenethyl or aryloxy .
  • Aryl is, for example, naphthyl, anthryl and preferably optionally substituted phenyl, the substituents only having to be considered for their inertness to the carboxylation reaction, otherwise they can be varied widely and include all inert C-organic radicals such as C 1 -C 6 -alkyl radicals , e.g. methyl, carboxyl residues such as COOH, COOM (M is for example a
  • the phosphine complexes can be prepared in a manner known per se, for example as described in the documents mentioned at the outset. For example, one starts from customary commercially available metal salts such as PdCl 2 or Pd (OCOCH 3 ) 2 and adds the phosphine, for example P (C 6 H 5 ) 3 , P (nC 4 H 9 ) 3 , PCH 3 (C 6 H 5 ) 2 ,
  • the amount of phosphine, based on the transition metal is usually 0 to 20, in particular 0.1 to 10 mol equivalents, particularly preferably 1 to 5 mol equivalents.
  • the amount of transition metal is not critical. Of course, for reasons of cost, you will rather get a small amount, e.g. from 0.1 to 10 mol%, in particular 1 to 5 mol%, based on the starting material II or III.
  • the reaction is carried out with carbon monoxide and at least equimolar amounts of water, based on the starting materials VI.
  • the reactant water can also serve as a solvent, i.e. the maximum amount is not critical.
  • Inert solvents which are customary for carboxylation reactions, such as hydrocarbons, for example toluene, xylene, hexane, pentane, cyclohexane, ethers, for example methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, substituted amides such as dimethylformamide, per-substituted ureas such as tetra-C 1 -C 4 alkylureas or nitriles such as benzonitrile or acetonitrile.
  • one of the reactants, in particular the base is used in excess, so that no additional solvent is required.
  • Bases suitable for the process are all inert bases which are able to bind the hydrogen iodide or hydrogen bromide released during the reaction.
  • tertiary amines such as tert-alkylamines, for example trialkylamines such as triethylamine, cyclic amines such as N-methylpiperidine or N, N'-dimethylpiperazine, pyridine, alkali metal or hydrogen carbonates, or tetraalkyl-substituted urea derivatives such as tetra-C 1 -C 4 - alkyl urea, for example tetramethyl urea.
  • the amount of base is not critical, usually 1 to 10, in particular 1 to 5, moles are used.
  • the amount is usually measured so that the reactants are dissolved, avoiding unnecessarily high excesses for reasons of practicality in order to save costs, to use small reaction vessels and to ensure maximum contact for the reactants.
  • the carbon monoxide pressure at room temperature is preferably 1 to 250 bar, in particular 5 to 150 bar CO.
  • the carbonylation is generally carried out continuously or batchwise at temperatures from 20 to 250 ° C., in particular at 30 to 150 ° C.
  • carbon monoxide is expediently pressed continuously onto the reaction mixture in order to maintain a constant pressure.
  • aryl halogen compounds VII used as starting compounds are known or can easily be prepared by a suitable combination of known syntheses and reaction sequences described above.
  • L M hydrogen, C 1 -C 6 -alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3 -Methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1 , 2-dimethylbutyl, 1,3-dimethylbutyl,
  • C 2 -C 6 alkynyl such as propargyl, 2-butynyl, 3-butenyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl- 2-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3 pentynyl, 1-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl,
  • C 1 -C 4 alkoxy such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy, in particular C 1 -C 3 alkoxy such as methoxy, ethoxy , i-Propoxy, where these groups can optionally be substituted by one to five halogen atoms such as fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine or C 1 -C 4 alkoxy as mentioned above.
  • halogen atoms such as fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine or C 1 -C 4 alkoxy as mentioned above.
  • the group defined above - (A) m -S (O) n R 1 represents , for example, C 1 -C 4 -alkylthio such as methylthio, ethylthio, n-propylthio, 1-methylethylthio, n-butylthio, 1-methylpropylthio, 2- Methylpropylthio and 1,1-dimethylethylthio, especially methylthio; C 1 -C 4 alkylsulfinyl such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, 1-methylethylsulfinyl, n-butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl and 1,1-dimethylethylsulfinyl, especially methylsulfinyl; C 1 -C 4
  • NC 1 -C 4 alkylsulfamoyl such as N-methylsulfamoyl, N-ethylsulfamoyl, Nn-propylsulfamoyl, N-1-methylethylsulfamoyl, Nn-butylsulfamoyl, N-1-methylpropylsulfamoyl, N-2-methylpropylsulfamoyl, N-2-methylpropylsulfamoyl especially N-methylsulfamoyl;
  • NC 1 -C 4 alkylsulfinamoyl such as N-methylsulfinamoyl, N-ethylsulfinamoyl, Nn-propylsulfinamoyl, N-1-methylethylsulfinamoyl, Nn-butylsulfinamoyl, N-1-methylpropylsulfinamoyl, N-2-methylproylmoylmethylsulfinamoyl especially N-methylsulfinamoyl; Di-C 1 -C 4 alkylsulfamoyl such as dimethylsulfamoyl, diethylsulfamoyl, dipropylsulfamoyl, dibutylsulfamoyl, N-methyl-N-ethylsulfamoyl, N-methyl-N-propylsulfamoyl, N-methyl-N-1-methylethy
  • C 1 -C 4 alkylsulfinyloxy such as methylsulfinyloxy, ethylsulfinyloxy, n-propylsulfinyloxy, 1-methylethylsulfinyloxy, n-butylsulfinyloxy, 1-methylpropylsulfinyloxy, 2-methylpropylsulfinyloxy and 1,1-dimethylethylsulfinyloxy, especially methylsulfinyloxy;
  • C 1 -C 4 alkylsulfonyloxy such as methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, 1-methylethylsulfonyloxy, n-butylsulfonyloxy, 1-methylpropylsulfonyloxy, 2-methylpropylsulfonyloxy and 1,1-dimethylethylsulfonyloxy, especially methylsulfonyloxy;
  • C 1 -C 4 alkylsulfinylamino such as methylsulfinylamino, ethylsulfinylamino, n-propylsulfinylamino, 1-methylethylsulfinylamino, n-butylsulfinylamino, 1-methylpropylsulfinylamino, 2-methylpropylsulfinylamino and 1, 1-dimethylethylsulfinylamino, in particular;
  • C 1 -C 4 alkylsulfonylamino such as methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, 1-methylethylsulfonylamino, n-butylsulfonylamino, 1-methylpropylsulfonylamino, 2-methylpropylsulfonylamino and 1,1-dimethylamino, especially 1,1-dimethylamino; NC 1 -C 4 alkylsulfinyl-N-methyl-amino such as N-methylsulfinyl-N-methyl-amino, N-ethylsulfinyl-N-methyl-amino, Nn-propylsulfinylN-methyl-amino, N-1-methylethylsulfinyl-N- methyl-amino,
  • N-n-butylsulfinyl-N-methyl-amino N-1-methylpropylsulfinyl-N-methyl-amino, N-2-methylpropylsulfinyl-N-methyl-amino and
  • NC 1 -C 4 alkylsulfinyl-N-ethylamino such as N-methylsulfinyl-N-ethylamino, N-ethylsulfinyl-N-ethylamino, Nn-propylsulfinyl-N-ethylamino, N-1-methylethylsulfinyl-N-ethylamino amino, Nn-butylsulfinylN-ethyl-amino, N-1-methylpropylsulfinyl-N-ethyl-amino,
  • NC 1 -C 4 alkylsulfonyl-N-methyl-amino such as N-methylsulfonyl-N-methyl-amino, N-ethylsulfonyl-N-methyl-amino, Nn-propylsulfonylN-methyl-amino, N-1-methylethylsulfonyl-N- methyl-amino,
  • N-n-butylsulfonyl-N-methyl-amino N-1-methylpropylsulfonyl-N-methyl-amino, N-2-methylpropylsulfonyl-N-methyl-amino and
  • NC 1 -C 4 alkylsulfonyl-N-ethylamino such as N-methylsulfonyl-N-ethylamino, N-ethylsulfonyl-N-ethylamino, Nn-propylsulfonyl-N-ethylamino, N-1-methylethylsulfonyl-N-ethylamino amino, Nn-butylsulfonyl-N-ethyl-amino, N-1-methylpropylsulfonyl-N-ethyl-amino,
  • C 1 -C 4 haloalkylthio such as chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, chlorodifluoromethylthio,
  • Pentafluoroethylthio especially trifluoromethylthio.
  • the group - (A) m -CO-R 2 defined above stands for example for C 1 -C 4 alkylcarbonyl such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, 1-methylethylcarbonyl, n-butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl and 1 , 1-dimethylethylcarbonyl, especially methylcarbonyl;
  • C 1 -C 4 alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, 1-methylethoxycarbonyl, n-butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl and 1,1-dimethylethoxycarbonyl, especially methoxycarbonyl;
  • NC 1 -C 4 alkylcarbamoyl such as N-methylcarbamoyl, N-ethylcarbamoyl, Nn-propylcarbamoyl, N-1-methylethylcarbamoyl, Nn-butylcarbamoyl, N-1-methylpropylcarbamoyl, N-2-methylpropylcarbamoyl and N-1,1-dimethylethylcarbamoyl especially N-methylcarbamoyl; Di-C 1 -C 4 alkylcarbamoyl such as dimethylcarbamoyl, diethylcarbamoyl, dipropylcarbamoyl, dibutylcarbamoyl, N-methyl-N-ethylcarbamoyl, N-methyl-N-propylcarbamoyl, N-methyl-N-1-methylethylcarbamoyl, N-methyl
  • C 1 -C 4 alkylcarbonyloxy such as methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, 1-methylethylcarbonyloxy, n-butylcarbonyloxy, 1-methylpropylcarbonyloxy, 2-methylpropylcarbonyloxy and 1,1-dimethylethylcarbonyloxy, especially methylcarbonyloxy;
  • C 1 -C 4 alkylcarbonylamino such as methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, 1-methylethylcarbonylamino,
  • n-butylcarbonylamino 1-methylpropylcarbonylamino, 2-methylpropylcarbonylamino and 1,1-dimethylethylcarbonylamino, especially methylcarbonylamino;
  • NC 1 -C 4 -alkylcarbonyl-N-methyl-amino such as N-methylcarbonyl- 1 -N-methyl-amino, N-ethylcarbonyl-N-methyl-amino, Nn-propylcarbonyl-N-methyl-amino, N-1-methylethylcarbonyl- N-methylamino,
  • N-n-butylcarbonyl-N-methyl-amino N-1-methylpropylcarbonyl-N-methyl-amino, N-2-methylpropylcarbonyl-N-methyl-amino and
  • X stands for:
  • C N-OCH 2 C ⁇ CH
  • C N-OCH 2 C ⁇ CCH3
  • C N-OCH 2 C 6 H 5 , CH-NH (OCH 3 ), CH-NH (OC 2 H 5 ),
  • C NN ((C 2 H 5 ) 2 ), CH-SCH 3 , CH-SC 2 H 5 , CH-SC 3 H 7 , CH-SC 4 H 9 , CH-SPr, CH-SiBu, CH-SH , C (CH 3 ) -SCH 3 , C (CH 3 ) -SC 2 H 5 , C (CH 3 ) -SC 3 H 7 ,
  • Phenyldiketone derivatives of the formula Ia are preferred,
  • L represents hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl
  • L is C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl,
  • phenyldiketone derivatives of the formula I in which the radicals L and M are hydrogen, methyl, methoxy, chlorine,
  • Phenyldiketone derivatives of the formula Ic are preferred,
  • L represents hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl
  • Cyano is and R 15 , n, Y and R 22 , R 21 , R 12 and R 13 have the meanings given above.
  • L represents hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl
  • Cyano is and R 15 , n, Y and R 12 and R 13 have the meanings given above.
  • Phenyldiketone derivatives of the formula Ie are also preferred.
  • L represents hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl
  • M is hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy,
  • C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, halogen, nitro or cyano and R 15 , n, Y and R 12 and R 13 have the meanings given above.
  • phenyldiketone derivatives of the formula I in which n is one or two and Y is CR 7 -OR 8 , where R 7 and R 8 have the meaning given above. Examples of particularly preferred compounds of the general formula I are compiled in the following tables.
  • Diazonium solution is carefully added dropwise. It is stirred for 1 hour. Then 106 g (2.65 mol) of sodium hydroxide in 270 ml of water are added, the mixture is stirred for a further 2 hours, the solution is acidified with hydrochloric acid and the precipitate formed is filtered off with suction. The solid is washed with water and dried.
  • the resulting precipitate is filtered off, washed with water and dried.
  • reaction solution is poured onto ice water and extracted with ethyl acetate.
  • organic phase is dried and then concentrated.
  • the product is purified by chromatography.
  • the compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides.
  • the herbicidal compositions containing I control vegetation very well on non-cultivated areas, particularly when high amounts are applied. In crops such as wheat, rice, corn, soybeans and cotton, they act against weeds and grass weeds without significantly damaging the crop plants. This effect occurs especially at low application rates.
  • the compounds I or compositions containing them can also be used in a further number of crop plants for eliminating undesired plants.
  • the following crops are considered, for example:
  • napobrassica Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis
  • the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
  • the herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active ingredients are less contractual for certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers, that the leaves of the sensitive crops are not hit, if possible, while the active ingredients reach the leaves of unwanted plants growing underneath or the uncovered area of the soil (post-directed, lay-by).
  • the compounds I or the herbicidal compositions comprising them can be sprayed or atomized, for example in the form of directly sprayable aqueous solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusting agents, scattering agents or granules , Dusting, scattering or pouring.
  • the application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • mineral oil fractions such as kerosene or diesel oil, also coal tarols and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol,
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • the substrates as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
  • alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g. Lignin-,
  • Powders, materials for spreading and dusting can be produced by mixing or grinding the active substances together with a solid carrier.
  • Granules e.g. Coated granules, impregnated granules and homogeneous granules can be produced by binding the active ingredients to solid carriers.
  • Solid carrier materials are mineral earths such as silica, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Urea and vegetable products such as flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • the concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range.
  • the formulations generally contain 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • the compounds I according to the invention can be formulated, for example, as follows:
  • Dissolved mixture consisting of 40 parts by weight of cyclohexanone
  • Dissolved mixture which consists of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction from the boiling point 210 to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of ricinusol. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient. IV 20 parts by weight of active ingredient No. 1.92 are with
  • Dissolved mixture which consists of 80 parts by weight of cyclohexanone and 20 parts by weight of Emulphor EL.
  • a stable emulsion concentrate is obtained.
  • the phenyldiketone derivatives I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together.
  • the application rates of active ingredient are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance depending on the aim of the control, the season, the target plants and the growth stage (a.s.)
  • Plastic flower pots with loamy sand with about 3.0% humus as a substrate served as culture vessels.
  • the seeds of the test plants were sown separately according to species.
  • the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles.
  • the vessels were lightly sprinkled, to encourage germination and growth, and then covered with clear plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients.
  • test plants For the purpose of post-emergence treatment, the test plants, depending on the growth habit, are first grown to a height of 3 to 15 cm and only then treated with the active ingredients suspended or emulsified in water. The test plants are either sown directly and grown in the same containers, or they are first grown separately as seedlings and transplanted into the test containers a few days before the treatment.
  • the application rate for post-emergence treatment was 0.5 or
  • the plants were kept at temperatures of 10 - 25 ° C or 20 - 35 ° C depending on the species.
  • the trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to the individual treatments was evaluated.
  • the plants used in the greenhouse experiments are composed of the following types:

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  • Chemical & Material Sciences (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
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Abstract

L'invention concerne des dérivés de dicétone phénylique de la formule (I) dans laquelle les substituants ont la notation suivantes: L, M désignent hydrogène, alkyle C1-C6, alkényle C2-C6, alkinyle C2-C6, alcoxy C1-C4, ces groupes pouvant éventuellement être substitués par un à cinq atomes d'halogène ou par alcoxy C1-C4; halogène, cyano, nitro, un groupe -(A)m-S(O)nR1 ou un groupe -(A)¿m-CO-R?2; Y désigne un groupe comprenant C=O, C=N-R?3, CR7-NR5R6, CR7-OR8, CR10CR11, CR7-OR8¿, 1,3 dioxanyle substitué par hydrogène ou alkyle C¿1?-C4 ou 1,3 dioxolanyle; un hétéroatome sélectionné dans le groupe oxygène, soufre et azote; X désigne une chaîne (-CR?12R13¿-), (-CR?12CR13-CR21R22-), (CR12=CR13¿-), (-CR?12R13-CR12=CR13-); NR23¿, la liaison entre X et Y pouvant être saturée ou insaturée; A désigne =, NR14; m vaut zéro ou un; n vaut zéro, un ou deux; R15 désigne cyclopropyle, 1-méthylcylopropyle; 1-méthylthiocyclopropyle ou butyle tert.; lorsque Y = C=O, X est différent de NR?23. R1 à R14 et R16 à R23¿ ont la notation mentionnée dans la revendication 1. L'invention concerne en outre des procédés de préparation de ces dérivés de dicétone phénylique, des agents les contenant, ainsi que leur utilisation ou celle des agents les contenant, pour lutter contre les graminées adventices/mauvaises herbes.
PCT/EP1996/005065 1995-11-23 1996-11-18 Derives de 2-cyano-1,3-dione, leur preparation et leur utilisation comme herbicides WO1997019071A1 (fr)

Priority Applications (1)

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AU76269/96A AU7626996A (en) 1995-11-23 1996-11-18 2-cyano-1,3-dione derivatives, the production of same and their use as herbicides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19543641.5 1995-11-23
DE1995143641 DE19543641A1 (de) 1995-11-23 1995-11-23 Phenyldiketonderivate

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0918056A1 (fr) * 1997-11-20 1999-05-26 Rhone-Poulenc Agriculture Ltd. Herbicides

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0496630A1 (fr) * 1991-01-25 1992-07-29 Rhone-Poulenc Agriculture Ltd. Herbicides à base de 2-cyano-1,3-dione
EP0496631A1 (fr) * 1991-01-25 1992-07-29 Rhone-Poulenc Agriculture Ltd. Herbicides à base de 2-cyano-1,3-dione
EP0625505A2 (fr) * 1993-05-18 1994-11-23 Rhone Poulenc Agriculture Ltd. Dérivés de 2-cyano-1,3-dione et leur emploi en tant qu'herbicides
EP0625508A2 (fr) * 1993-05-18 1994-11-23 Rhone Poulenc Agriculture Ltd. Dérivés de 2-cyano-1,3 dione contenant du soufre et leur emploi en tant qu'herbicides
WO1995025099A1 (fr) * 1994-03-17 1995-09-21 Rhone-Poulenc Agriculture Ltd. Derives de 2-cyano-1,3-dione utiles en tant qu'herbicides
WO1996005183A1 (fr) * 1994-08-08 1996-02-22 Basf Aktiengesellschaft Derives saccharine et leur utilisation comme herbicides
WO1996026193A1 (fr) * 1995-02-24 1996-08-29 Basf Aktiengesellschaft Derives de phenyldicetone

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0496630A1 (fr) * 1991-01-25 1992-07-29 Rhone-Poulenc Agriculture Ltd. Herbicides à base de 2-cyano-1,3-dione
EP0496631A1 (fr) * 1991-01-25 1992-07-29 Rhone-Poulenc Agriculture Ltd. Herbicides à base de 2-cyano-1,3-dione
EP0625505A2 (fr) * 1993-05-18 1994-11-23 Rhone Poulenc Agriculture Ltd. Dérivés de 2-cyano-1,3-dione et leur emploi en tant qu'herbicides
EP0625508A2 (fr) * 1993-05-18 1994-11-23 Rhone Poulenc Agriculture Ltd. Dérivés de 2-cyano-1,3 dione contenant du soufre et leur emploi en tant qu'herbicides
WO1995025099A1 (fr) * 1994-03-17 1995-09-21 Rhone-Poulenc Agriculture Ltd. Derives de 2-cyano-1,3-dione utiles en tant qu'herbicides
WO1996005183A1 (fr) * 1994-08-08 1996-02-22 Basf Aktiengesellschaft Derives saccharine et leur utilisation comme herbicides
WO1996026193A1 (fr) * 1995-02-24 1996-08-29 Basf Aktiengesellschaft Derives de phenyldicetone

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0918056A1 (fr) * 1997-11-20 1999-05-26 Rhone-Poulenc Agriculture Ltd. Herbicides

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DE19543641A1 (de) 1997-05-28
AR004743A1 (es) 1999-03-10

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